WO2007108243A1 - Optical film, method and apparatus for producing same, polarizing plate, and liquid crystal display - Google Patents

Optical film, method and apparatus for producing same, polarizing plate, and liquid crystal display Download PDF

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Publication number
WO2007108243A1
WO2007108243A1 PCT/JP2007/052227 JP2007052227W WO2007108243A1 WO 2007108243 A1 WO2007108243 A1 WO 2007108243A1 JP 2007052227 W JP2007052227 W JP 2007052227W WO 2007108243 A1 WO2007108243 A1 WO 2007108243A1
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WO
WIPO (PCT)
Prior art keywords
film
optical film
plasticizer
group
polarizing plate
Prior art date
Application number
PCT/JP2007/052227
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French (fr)
Japanese (ja)
Inventor
Noriki Tachibana
Original Assignee
Konica Minolta Opto, Inc.
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Publication date
Application filed by Konica Minolta Opto, Inc. filed Critical Konica Minolta Opto, Inc.
Priority to JP2008506192A priority Critical patent/JP5024284B2/en
Publication of WO2007108243A1 publication Critical patent/WO2007108243A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/31—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets being adjustable, i.e. having adjustable exit sections
    • B29C48/313—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets being adjustable, i.e. having adjustable exit sections by positioning the die lips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/355—Conveyors for extruded articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3475—Displays, monitors, TV-sets, computer screens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • OPTICAL FILM OPTICAL FILM, MANUFACTURING METHOD THEREOF, ITS MANUFACTURING DEVICE, POLARIZING PLATE, LIQUID CRYSTAL DISPLAY DEVICE
  • the present invention relates to an optical film, a production method thereof, a production apparatus thereof, a polarizing plate, and a liquid crystal display device, and more specifically, a flat surface produced by heating and melting a melt containing cellulose ester resin and a plasticizer.
  • the present invention relates to an optical film having excellent properties and optical properties, a production method thereof, a production apparatus thereof, a polarizing plate, and a liquid crystal display device.
  • an optical film is provided on the outermost surface of a liquid crystal display or a plasma display by providing a protective film for a polarizing plate of a liquid crystal display, an antireflection layer, an antiglare layer, and a hard coat layer.
  • Optical films have high transparency, flatness, moisture permeation prevention, bleed-out resistance, dimensional stability (does not vary with temperature and humidity and time), and adhesion to PVA polarizing films used for polarizing plates. Various performances are required.
  • Cellulose ester films for optical use are generally used as polarizing plate protective films because of their adhesion to PVA polarizing films used in polarizing plates and appropriate moisture permeation prevention properties.
  • Manufactured by a solution casting method using an organic solvent is being restricted in terms of environmental and safety aspects.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-352620
  • Patent Document 2 JP-A-2005-178194
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-182979
  • an object of the present invention is to produce an optical film excellent in flatness and optical properties, produced by heat-melting a melt containing cellulose ester resin and a plasticizer, a production method thereof, an apparatus for producing the same, and The object is to provide a polarizing plate and a liquid crystal display device.
  • an optical film produced by heating and melting a melt containing cellulose ester resin and a plasticizer, having excellent flatness and optical properties, a production method and production apparatus thereof, a polarizing plate, and a liquid crystal display A device can be provided.
  • FIG. 1 is a cross-sectional view of a manufacturing apparatus according to the present invention.
  • the optical film of the present invention was cast into a film shape according to a method for producing an optical film in which at least cellulose ester resin and a plasticizer were melted by heating and cast into a film shape. After that, it is characterized by water treatment.
  • water treatment refers to immersing a film formed by casting into a roll-shaped film in a water tank filled with water for a predetermined time until winding.
  • water for water treatment pure water, distilled water, ion-exchanged water, tap water and the like which can be usually used industrially can be used.
  • the temperature of water used for water treatment is not less than room temperature and not more than 100 ° C, preferably 50-9.
  • the water treatment time can be appropriately determined according to various conditions such as film thickness.
  • a film of 20 to 120 / ⁇ ⁇ it can be selected in the range of 1 to 120 minutes, preferably 5 to 70 minutes.
  • the water tank for water treatment may be separated into one or more tanks.
  • the point of process control is preferably 4 tanks or less. When multiple tanks are used, it is preferable to drain water at the place where the tanks are switched. In addition, in order to avoid mixing water in each tank, it may be separately washed with a shower. After passing through the last water tank, it is preferable to dry the film.
  • Water for water treatment may contain additives such as salts, surfactants, wrinkle adjusters, preservatives, etc. Can be selected as appropriate
  • the water used for water treatment oozes out additives in the film over time. It will be contaminated with water, but it is possible to measure the degree of contamination as appropriate and replace it with new water. It is also possible to use a circulation purifier.
  • the film While being immersed in a water tank for water treatment, the film is preferably held in width by a tenter or the like. Moreover, it is preferable to carry out an extending
  • melt casting in the present invention is defined as melt casting in which a cellulose ester is heated and melted to a temperature exhibiting fluidity without using a solvent, and then the fluid cellulose ester is cast.
  • the molding method for heating and melting can be further classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretch molding method.
  • the melt extrusion method is excellent for obtaining an optical film excellent in mechanical strength and surface accuracy.
  • extrusion film formation on a drum or endless belt is included in the method for producing a cellulose ester film of the present invention as a melt casting film formation method. It is.
  • a water-soluble plasticizer is one whose lOOg dissolved in pure water at 25 ° C is 5g or more. Preferably, it is 7 g or more.
  • the plasticizer of the present invention is preferably used by mixing a hydrophobic plasticizer with a water-soluble plasticizer.
  • Hydrophobic plasticizers are those whose lOOg dissolved in pure water at 25 ° C is less than 5 g. Preferably, it is 3 g or less.
  • a plasticizer that can be generally used as a protective film for a polarizing plate can be appropriately employed.
  • phosphoric acid ester derivatives and carboxylic acid ester derivatives are preferably used.
  • a polymer obtained by polymerizing an ethylenically unsaturated monomer having a weight average molecular weight of 500 or more and 10,000 or less described in JP-A-2003-12859, an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, or An acrylic polymer having a cyclohexyl group in the side chain is also preferably used.
  • the water-soluble plasticizer and the hydrophobic plasticizer of the plasticizer of the present invention are structurally similar! Therefore, the compound power of the same strain can be selected as appropriate depending on the difference in water solubility.
  • the alcohol compound used in the present invention is not particularly limited, and monovalent to polyvalent alcohol compounds can be used.
  • the monohydric alcohols include butyl alcohol, (iso- or n-) aminoleanolone, hexinoreanoreconole, heptinoleanoreconole, 1-octanol, 2 — Diethyl alcohols such as ethylhexyl alcohol, n-dodecyl alcohol, lauryl alcohol, and oleyl alcohol include 1,5-pentadiol, ethylene glycol, propylene glycol, 2-methyl 2,4 pentadiol, 1, 6 -Trivalent alcohols such as hexanediol, trimethylolpropane, trimethylolethane, glycerin, phytanetriol, etc., tetravalent alcohols such as pentaerythritol, diglycerin, etc. Polyglycerin is mentioned.
  • the boiling point is preferably 160 ° C or higher.
  • the number of C is less than 7, if the boiling point and flash point are low and the boiling point is lower than 160 ° C, process contamination with significant volatilization during heat molding becomes a problem.
  • Substances with a flash point of 60 ° C or lower are also classified as dangerous goods, and they are classified as Class 4 No. 2 petroleums (special flammables, 1 stone) under the Fire Service Law and are extremely dangerous.
  • bleed-out resistance deteriorates due to water solubility.
  • alcohol compounds heptyl alcohol, 1-octanol, 2-ethylhexyl alcohol, n-dodecyl alcohol, lauryl alcohol, oleyl alcohol and the like are preferable alcohol compounds for obtaining the effects of the present invention. .
  • the melting point is 60 ° C or lower and the boiling point is 160 ° C or higher.
  • the melting point exceeds 70 ° C, the melting point lowering effect and the melt viscosity lowering effect are reduced.
  • the boiling point is lower than 160 ° C, volatilization will be significant during heat molding. Process contamination becomes a problem.
  • Examples of the phosphoric acid ester derivative include a phosphoric acid ester plasticizer, an ethylene glycol ester plasticizer, a glycerin ester plasticizer, a diglycerin ester plasticizer (fatty acid ester), and a polyhydric alcohol.
  • Examples thereof include ester plasticizers, dicarboxylic acid ester plasticizers, polycarboxylic acid ester plasticizers, and polymer plasticizers.
  • ester plasticizers dicarboxylic acid ester plasticizers, polycarboxylic acid ester plasticizers, and polymer plasticizers.
  • polyhydric alcohol ester plasticizers, dicarboxylic acid ester plasticizers, and polycarboxylic acid ester plasticizers are preferred.
  • the plasticizer may be liquid or solid, and it is preferable that the plasticizer is colorless because of restrictions on the composition.
  • the decomposition initiation temperature is preferably 150 ° C or higher, more preferably 200 ° C or higher, which is preferably stable at higher temperatures.
  • the addition amount can be adjusted for various performances required for the optical film, and the blending amount thereof is appropriately selected within the range not impairing the object of the present invention, and is preferably 1 with respect to 100 parts by mass of the cellulose ester resin. -50 mass%, more preferably 3-30 mass%. 5 to 15% by mass is particularly preferable.
  • plasticizer used in the present invention will be further described. Specific examples are not limited to these examples.
  • Phosphoric ester plasticizers specifically, phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate, and triphenyl- Ruphosphate, tricresyl phosphate, credinole-nore phosphate, otachinoresphie-nore phosphate, diphenol dirubibinenophosphate, trioctinorephosphate, tribubutinorephosphate, trinaphthyl phosphate, trixylyl phosphate, trisorthophosphate And phosphoric acid aryl ester.
  • These substituents may be the same or different, and may be further substituted. Also, it may be a mix of alkyl, cycloalkyl, and aryl groups, and the substituents may be covalently bonded.
  • ananolene bis ethylene bis (dimethyl phosphate), butanolene bis (diethyl quinolephosphate), ethylene bis (diphenol-phosphate phosphate), propylene bis (dinaphthinorephosphate), etc.
  • Diarynophosphate Huerlenbis (Dibutinorephosphate), Bi-Lenbis (Di-Cutinorephosphate), etc.
  • phosphate esters such as arylene bis (diaryl phosphate) such as arylene bis (diolequinophosphate;), phenylene bis (diphenyl phosphate), and naphthylene bis (ditolyl phosphate).
  • substituents may be the same or different, and may be further substituted. Also, it may be a mix of alkyl, cycloalkyl, and aryl groups, and the substituents may be covalently bonded.
  • phosphate ester Part of polymer or part of molecular structure of additives such as antioxidants, acid scavengers, UV absorbers etc. May be introduced.
  • additives such as antioxidants, acid scavengers, UV absorbers etc.
  • phosphoryl ester and arylene bis (diaryl phosphate) are preferred.
  • triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferred.
  • Ethylene glycol ester-based plasticizer Specifically, ethylene glycol dioleopropylene ester plasticizer such as ethylene glycol diacetate and ethylene glycol dibutyrate, ethylene glycol dicyclopropyl carboxylate And ethylene glycol cycloalkyl ester plasticizers such as ethylene glycol dicyclohexylcarboxylate, and ethylene glycol diaryl ester plasticizers such as ethylene glycol dibenzoate and ethylene glycol di-4-methylenobenzoate. . These alkylate group, cycloalkylate group and arylate group may be the same or different, and may be further substituted.
  • ethylene glycol ester may have a substituted partial structure strength of an ethylene glycol ester. It may be part of a polymer or may be regularly pendant. Also, an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into a part of the molecular structure of the additive.
  • Glycerin ester plasticizers specifically glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, glycerol tricyclopropyl carboxylate, glycerol tricyclohexyl carboxylate Glycerin cycloalkyl ester, glycerin tribenzoate, glycerin 4-methylbenzoate, etc.
  • glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, glycerol tricyclopropyl carboxylate, glycerol tricyclohexyl carboxylate
  • Glycerin cycloalkyl ester specifically glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate capry
  • glycerin aryl ester diglycerin tetraacetyl
  • Diglycerin cycloalkyl esters such as diglycerin alkyl esters such as diglycerin tetrapropionate, diglycerin acetate tricaprylate, diglycerin tetralaurate, diglycerin tetracyclobutyl carboxylate, diglycerin tetracyclopentyl carboxylate
  • diglycerin tetrabenzoate such as diglycerin tetrabenzoate and diglycerin 3-methylbenzoate.
  • These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted.
  • glycerin ester and diglycerin part may be substituted glycerin ester, diglycerin ester partial structural strength part of polymer, or may be regularly bent, also antioxidant, acid scavenger It may be introduced into a part of the molecular structure of additives such as UV absorbers.
  • Polyhydric alcohol ester plasticizer Specific examples include polyhydric alcohol ester plasticizers described in paragraphs 30 to 33 of JP-A No. 2003-12823.
  • alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted.
  • a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group may be used, and these substituents may be covalently bonded.
  • the polyhydric alcohol part may be substituted! Partial polyhydric alcohol structure may be part of the polymer or may be regularly pendant Antioxidants, acid scavengers, UV absorbers It may be introduced into a part of the molecular structure of the additive.
  • Dicarboxylic acid ester plasticizer Specifically, alkyl dicarboxylic acid alkyl ester plasticizer such as didodecyl malonate (C1), dioctyl adipate (C4), dibutyl sebacate (C8), Alkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclopentyl succinate and dicyclohexyl adipate, alkyl dicarboxylic acid aryl ester plasticizers such as diphenyl succinate and di-4-methylphenol glutarate, dihexyl , 4-cyclohexanedicarboxylate, didecyl bicyclo [2.2.1] heptane 2,3 dicarboxylate Alkyl ester plasticizers such as dicyclohexyl 1,2-cyclobutane dicarboxylate and dicyclopropinole 1,2-cyclohexinoresiency nore oxylate, and the like.
  • alkoxy groups and cycloalkoxy groups may be the same or different, and may be mono-substituted. These substituents may be further substituted.
  • the alkyl group and cycloalkyl group may be mixed, or these substituents may be covalently bonded.
  • the aromatic ring of phthalic acid may be substituted and may be a multimer such as a dimer, trimer or tetramer. It is also part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc., which may be partly polymerized or partially pendant into the polymer. It is okay to be introduced.
  • Polycarboxylic acid ester plasticizers Specifically, alkyl polyhydric strengths such as tridodecyl triforce ruvalate, tributyl meso butane-1, 2, 3, 4-tetracarboxylate, etc.
  • Alkyl polyvalent carboxylic acid cycloalkyl ester based plasticizers such as tricyclohexyl triforce ruvalate, tricyclopropyl-2-hydroxy-1, 2, 3 propane tricarboxylate, triphenyl 2-hydroxy 1, 2, 3 —propane
  • Alkyl polycarboxylic acid aryl ester plasticizers such as tricarboxylate, tetra-3-methylphenoltetrahydrofuran 1, 2, 3, 4, 5-tetracarboxylate, tetrahexyl 1,2,3,4-cyclobutane Tetracarboxylate, tetrabutyl — 1, 2, 3, 4-cyclopentanetetracarboxylate, etc.
  • Black alkyl polyhydric carboxyalkyl phosphate alkyl ester plasticizers tetra cyclopropyl 1, 2, 3, 4 Shikurobutan tetra force Norebokishireto, Kishinore 1, 3, 5 Kishinoretori force Norebokishi to cycloheteroalkyl tricyclo Cycloalkyl polycarboxylic acid cycloalkyl ester plasticizers such as rate, triphenyl 1, 3, 5 cyclohexyl tricarboxylate, hexamethyl 4-methylphenol 1, 2, 3, 4, 5, 6 Cycloalkyl polycarboxylic acid aryl ester plasticizers such as cyclohexylhexacarboxylate, tridodecylbenzene 1, 2, 4 tricarboxylate, tetraoctylbenzene 1, 2, 4, 5-tetracarboxylate, etc.
  • Alkyl polycarboxylic acid alkyl ester plasticizers tricyclopentylbenzene 1, 3, 5 tricarboxylate, tetracyclohexylbenzene 1, 2, 3, 5-tetra force polycarboxylic acid such as ruboxylate
  • Cycloalkyl ester plasticizers Triphenylbenzene 1, 3, 5-Tetracartoxylate, Hexa 4 Methylphenol Hmm 1, 2, 3, 4, 5, Ariru polycarboxylic acid ⁇ Li Ruesuteru based plasticizers hexa carboxylate to 6.
  • These alkoxy groups and cycloalkoxy groups may be the same or different and may be mono-substituted, and these substituents may be further substituted.
  • Alkyl groups and cycloalkyl groups may be mixed, and these substituents may be bonded together via a covalent bond!
  • the aromatic ring of phthalic acid may be substituted, and a polymer such as a good dimer, trimer or tetramer may be used.
  • the partial structure of the phthalate ester is introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc., which may be partly pendant into the polymer. It may be done.
  • Polymer plasticizers include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, acrylic polymers such as polyethyl acrylate and polymethyl methacrylate, polyvinyl isobutyl ether, and poly N-butyl. Buryl polymers such as pyrrolidone, styrene polymers such as polystyrene and poly-4-hydroxystyrene, polybutylene succinate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide, polyamides , Polyurethane, polyurea and the like.
  • the number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5000 to 200,000.
  • polymer plasticizers may be homopolymers with one type of repeating unit force.
  • the plasticizers it is generally preferable that no volatile component is generated during heat melting.
  • Specific examples include non-volatile phosphate esters described in JP-A-6-501040, and examples include arylene bis (diaryl phosphate) esters and trimethylolpropane tribenzoate among the above exemplified compounds. Although it is preferable, it is not limited to these.
  • the thermal decomposition temperature Td (l. 0) of the plasticizer is defined as the temperature at which the mass decreases by 1.0% by mass, than the melting temperature of the film-forming material. High is required.
  • the thermal decomposition temperature Td (l. 0) can be measured with a commercially available differential thermogravimetric analysis (TG—DTA) apparatus.
  • the cellulose ester resin according to the present invention shows the structure of cellulose ester and contains at least one structure selected from the group consisting of a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group. Preferred to be an ester.
  • aromatic ring is a benzene ring and the aromatic ring is a benzene ring
  • substituent of the benzene ring include a halogen atom, a cyanoalkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group.
  • R is aliphatic group, aromatic
  • a group or a heterocyclic group is preferably one to five, one to four, more preferably one to three, and even more preferably one or two. preferable.
  • Substituents include halogen atoms, cyanide alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, carbonamido groups, sulfonamido groups and ureido groups, halogen atoms, cyanide alkyl groups, alkoxy groups.
  • a halogen atom, an alkyl group, an alkoxy group, and an aryl group more preferably a halogen atom, an alkyl group, and an alkoxy group, more preferably a halogen atom, a silylated alkyl group, an alkoxy group, and an aryloxy group.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group may have a cyclic structure or a branch.
  • the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-12, even more preferably 1-6, and most preferably 1-4.
  • Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl.
  • the alkoxy group may have a cyclic structure or a branch.
  • the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-12, even more preferably 1-6, and most preferably 1-4.
  • the alkoxy group may be further substituted with another alkoxy group.
  • ⁇ J of the vinyloxy group includes methoxy, ethoxy, 2-methoxyethoxy, 2-methoxy-2-ethoxyethoxy, butoxy, hexyloxy and octyloxy.
  • the number of carbon atoms in the aryl group is preferably 6-20, and more preferably 6-12.
  • aryl groups include phenyl and naphthyl.
  • the number of carbon atoms in the ruoxy group is preferably 6-20, and more preferably 6-12.
  • the aryloxy group include phenoxy and naphthoxy.
  • the number of carbon atoms in the acyl group is preferably 1-20, and more preferably 1-12.
  • Examples of the acyl group include formyl, acetyl and benzoyl.
  • the number of carbon atoms of the carboxamide group is preferably 1-20, and more preferably 1-12.
  • Examples of the carbonamido group include acetamide and benzamide.
  • the number of carbon atoms of the sulfonamide group is preferably 1-20, and more preferably 1-12.
  • the sulfonamide group include methanesulfonamide, benzenesulfonamide, and p-toluenesulfonamide.
  • the number of carbon atoms of the ureido group is preferably 1-20, and more preferably 1-12.
  • Examples of ureido groups include (unsubstituted) ureido.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12.
  • aralkyl groups include benzyl, phenethyl and naphthylmethyl.
  • the alkoxycarbonyl group has preferably 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbon.
  • the number of carbon atoms of the aryloxycarbonyl group is preferably 7-20, and more preferably 7-12. Examples of aryloxy groups include phenoxycarbons.
  • the number of carbon atoms of the aralkyloxycarbonyl group is preferably 8 to 20, and more preferably 8 to 12.
  • Examples of the aralkyloxycarbonyl group include benzyloxycarbonyl.
  • the above-mentioned force The number of carbon atoms of the rubermoyl group is preferably 1-20, more preferably 1-12.
  • Examples of force rubamoyl groups include (unsubstituted) force rubamoyl and N-methylcarbamoyl.
  • the number of carbon atoms in the sulfamoyl group is preferably 20 or less, and more preferably 12 or less.
  • Examples of the sulfamoyl group include (unsubstituted) sulfamoyl and N-methylsulfamoyl.
  • the number of carbon atoms in the acyloxy group is preferably 1-20, and more preferably 2-12.
  • Examples of the acyloxy group include acetoxy and benzoyloxy.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 20, and preferably 2 to 12. Is more preferable.
  • alkenyl groups include vinyl, aryl and isopropyl.
  • the number of carbon atoms of the alkyl group is preferably 2-20, and more preferably 2-12.
  • alkyl groups include chaels.
  • the number of carbon atoms of the alkylsulfonyl group is preferably 1-20, and more preferably 1-12.
  • the number of carbon atoms in the arylaryl group is preferably 6-20, more preferably 6-12! /.
  • the number of carbon atoms of the alkyloxysulfol group is preferably 1-20, and more preferably 1-12.
  • the aryloxy sulfol group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the number of carbon atoms of the alkylsulfooxy group is preferably 1-20, and more preferably 1-12.
  • the number of carbon atoms of the aryloxysulfol group is preferably 6-20, and more preferably 6-12.
  • the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetylyl. Propionyl, butyryl, isobutyryl, valeryl, bivalol, hexanoyl, otatanyl, lauroyl, stearoyl and the like.
  • aliphatic acyl group is intended to include those further having a substituent.
  • substituents include a benzene ring when the aromatic ring is a benzene ring in the above-mentioned aromatic acyl group. What was illustrated as a substituent of is mentioned.
  • the esterified substituent of the cellulose ester is an aromatic ring
  • the number of substituents X substituted on the aromatic ring is 0 or 1 to 5, preferably 1 to 3. Particularly preferred is 1 or 2.
  • the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline). , Isoquinoline, chromene, chroman, phthalazine, atalidine, indole, indoline, etc.).
  • the cellulose of the present invention has a structure having a structure selected from at least one of a substituted or unsubstituted aliphatic acyl group and a substituted or unsubstituted aromatic acyl group in the cellulose ester. Used as a structure for esters, these may be cellulose single or mixed acid esters. May be used in combination.
  • cellulose ester constituting the optical film of the present invention
  • cellulose ester cellulose ester, cellulose ester, cellulose propionate, senorelose butyrate, senorelose acetate propionate and senocellulose acetate butyrate are particularly preferred!
  • cellulose acetate propionate and lower fatty acid ester of cellulose acetate butyrate have an acyl group having 2 to 4 carbon atoms as a substituent, and the degree of substitution of the acetyl group.
  • cellulose acetate propionate is particularly preferably used. Among them, 1.9 ⁇ ⁇ ⁇ 2.5, and preferably 0.1 ⁇ 0.9. If not substituted with the above acyl group, the moiety is usually present as a hydroxyl group. These can be synthesized by known methods.
  • the cellulose ester used in the present invention preferably has a weight average molecular weight MwZ number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 2.0 to 5.0. More preferably, it is 2.5 to 5.0, and a more preferably 3.0 to 5.0 cenorelose ester is preferably used.
  • the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter.
  • Wood pulp may be coniferous or hardwood, but coniferous is more preferred.
  • Cotton linter is also preferably used for the peelable point force during film formation. Cellulose esters made from these can be mixed appropriately or used alone.
  • cotton linter-derived cellulose ester wood pulp (coniferous) -derived cellulose Suester: The ratio of cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50: 50: 0, 20: 80: 0, 10: 90: 0, 0 : 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
  • the cellulose ester resin according to the present invention is charged into 20 ml of pure water (electrical conductivity of 0.1 ⁇ S / cm or less, pH 6.8) at 25 ° C, lhr, under a nitrogen atmosphere.
  • the pH is preferably 6 to 7, and the electric conductivity is 1 to: LOO / z SZcm. If the pH is less than 6, the residual organic acid may accelerate cellulose degradation during heating and melting, and if the pH is higher than 7, hydrolysis may accelerate.
  • the electrical conductivity is 100 SZcm or more, since a relatively large amount of residual ions are present, it may be a factor that deteriorates cellulose during heating and melting.
  • the antioxidant used in the present invention will be described.
  • antioxidants examples include phenol-based antioxidants, phosphorus-based antioxidants, phenol-based antioxidants, heat-resistant cache stabilizers, oxygen scavengers, and the like. Phenolic antioxidants, particularly alkyl-substituted phenolic acid inhibitors are preferred. By blending these anti-oxidation agents, coloring and strength reduction of the molded product due to heat and oxidative deterioration during molding can be prevented without reducing transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the amount of the antioxidant is appropriately selected within a range not impairing the object of the present invention.
  • the hindered phenol acid inhibitor compound is a known compound, and is described in, for example, columns 12 to 14 of US Pat. No. 4,839,405.
  • 2, 6-dialkylphenol derivative compounds, such as Such compounds include those of the following general formula (1).
  • [0075] [Chemical 1] —General formula (1)
  • Rl, R2 and R3 represent a further substituted force or an unsubstituted alkyl substituent.
  • Specific examples of hindered phenol compounds include n-octadecyl 3- (3,5-di-tert-butyl 4-hydroxyphenol) -propionate, n-octadecyl 3- (3,5-di-tert-butyl.
  • antioxidants include phosphorous antioxidants such as trisnoylphenol phosphite, triphenyl phosphite, tris (2,4 di-tert-butylphenol) phosphite, dilauryl 3, 3, 1-dipropionate, dimyristyl 3, 3, -thio dipropionate, distearyl 3, 3, 1-didipropionate, pentaerythrityl tetrakis (3 lauryl thiopropionate), etc.
  • phosphorous antioxidants such as trisnoylphenol phosphite, triphenyl phosphite, tris (2,4 di-tert-butylphenol) phosphite, dilauryl 3, 3, 1-dipropionate, dimyristyl 3, 3, -thio dipropionate, distearyl 3, 3, 1-didipropionate, pentaerythrityl tetrakis (3 lauryl thiopropionate), etc
  • tert-Butyl— 6 (3— tert-Butyl-2 hydroxy-5-methylbenzyl) —4-Methylphenol acrylate, 2— [1— (2 Hydroxy-3, 5 Di-tert-pentylphenol- R) Ethyl] 4, 6-di-tert-pentyl-phenol talate, etc., metathermal processing stabilizers, Japanese Patent Publication No.
  • the optical film according to the present invention preferably contains an organic additive in addition to cellulose ester resin, a plasticizer, an antioxidant and an alcohol compound.
  • Organic additives include acid scavengers, light stabilizers, UV absorbers, retardation control agents, and polymer materials.
  • the acid scavenger preferably comprises an epoxy compound as an acid scavenger described in US Pat. No. 4,137,201.
  • Epoxy compounds as such acid scavengers are known in the art and include condensation of various polyglycol diglycidyl ethers, particularly about 8-40 moles of ethylene oxide per mole of polyglycol.
  • Metal glycol epoxy compounds such as polyglycols derived from glycerol, diglycidyl ethers of glycerol (eg, those conventionally used in salt vinyl polymer compositions and with vinyl chloride polymer compositions), Epoxy ether condensation product, diglycidyl ether of bisphenol A (ie 4,4, -dihydroxydiphenol-dimethylmethane), epoxy ester unsaturated fatty acid ester (especially 2-22 of 4 fatty acids of this carbon atom) Esters of alkyls of up to about 2 carbon atoms (eg butylepoxy cysterate) , And various epoxy long chain fatty acid triglycerides and the like (eg, epoxidized vegetable oils and other unsaturated natural oils, which are represented and exemplified by compositions such as epoxy soybean oil, sometimes these These are called natural glycerides or unsaturated fatty acids, and these fatty acids generally contain 12 to 22 carbon atoms)). Particularly preferred are commercially available epoxy group-
  • n is equal to 0-12.
  • acid scavengers that can be used include those described in paragraphs 87 to 105 of JP-B-5-194788.
  • Light stabilizers include hindered amine light stabilizer (HALS) compounds, which are known compounds, such as columns 5-11 of U.S. Pat.No. 4,619,956 and U.S. Pat. 4, 839, 405, as described in columns 3-5, 2, 2, 6, 6-tetraalkylpiperidine compounds, or their acid addition salts or their metals Complexes with compounds are included.
  • HALS hindered amine light stabilizer
  • Such compounds include those of general formula (3) below.
  • R1 and R2 are H or a substituent.
  • Specific examples of hindered amine light stabilizer compounds include: 4-hydroxy-1,2,2,6,6-tetramethylpiperidine, 1-aryl-1, hydroxyl 2,2,6,6-tetramethylpiperidine, 1-benzyl 4-hydroxy-1,2,2,6,6-tetramethylpiperidine, 1- (4-tert-butyl-2-butyr) mono-4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy 2,2 , 6, 6-Tetramethylbiperidine, 1-ethyl-4-salicyloyloxy 2, 2, 6, 6-tetramethylpi Peridine, 4-methacryloyloxy-1, 2, 2, 6, 6 Pentamethylpiperidine, 1, 2, 2, 6, 6-Pentamethylpiperidine-4-yl j8 (3,5-di-tert-butyl-4-hydroxyphene- Propionate, 1 Benzyloxy-1, 2, 2, 6, 6 Pentamethylpiperidine,
  • These hindered amine light resistance stabilizers can be used alone or in combination of two or more, and these hindered amine light resistance stabilizers and plasticizers, acid scavengers, ultraviolet absorbers can be used. These additives may be used in combination or may be introduced into a part of the additive molecular structure.
  • the compounding amount is appropriately selected within the range not impairing the object of the present invention.
  • the cellulose ester resin preferably has a mass of 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass with respect to 100 parts by mass. Particularly preferred is 0.05 to 10 parts by mass.
  • an ultraviolet absorber it is excellent in the ability to absorb ultraviolet light with a wavelength of 370 nm or less from the viewpoint of preventing the polarizer and the display device from being deteriorated by ultraviolet light, and from the viewpoint of liquid crystal display, it absorbs visible light with a wavelength of 400 nm or more. Those with less are preferred. Examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, etc., but benzophenone compounds and less colored benzotriazole compounds Compounds are preferred. Also, use ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574, and polymer ultraviolet absorbers described in JP-A-6-148430.
  • UV absorbers include 2- (2'-hydroxy-5'-methylphenol) benzotriazole, 2- (2'-hydroxy-1 3 ', 5'-di-1 t ert—Butylphenol) benzotriazole, 2— (2 ′ —Hydroxy-3 ′ —tert—Butyl 5 '—methylphenol) benzotriazole, 2— (2 ′ —hydroxyl 3 ′, 5′-di-tert butylphenol) 5 clobenzobenzotriazole, 2— (2 ′ —hydroxy-3 ′ — (3 ", 5 Q" —tetrahydrophthalimidomethyl) 5, —methylphenyl) benzotriazole, 2, 2-methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) —6 — (2H benzotriazole 2- 2) (2'-hydroxy 1 3 'tert-butyl 5'-methyl phenol) 5 clobenzobenzotriazole, 2-
  • TINUVIN 109 TINUVIN 171
  • TINUVIN 360 manufactured by Specialty One Chemicals Co., Ltd.
  • benzophenone compounds include 2, 4 dihydroxybenzophenone, 2, 2 '
  • 0.1 to 20% by mass of the UV absorber is preferably added, and more preferably 0.5 to: 15% by mass of LO is preferably added. Is preferred. Two or more of these may be used in combination.
  • an alignment film is formed to provide a liquid crystal layer, and a polarizing plate protective film and a retardation derived from the liquid crystal layer are combined to provide an optical compensation capability, thereby providing a liquid crystal display quality.
  • the polarizing plate may be processed so as to improve this.
  • the compound added to adjust the retardation is an aromatic compound having two or more aromatic rings as described in the specification of European Patent 911, 656A2, which is used as a retardation control agent. You can also Two or more aromatic compounds may be used in combination.
  • the aromatic ring includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
  • Aromatic heterocycles that are particularly preferred to be aromatic heterocycles are generally unsaturated heterocycles. Of these, a 1, 3, 5-triazine ring is particularly preferred.
  • polymer materials other than cellulose esters and oligomers may be appropriately selected and mixed.
  • the polymer materials and oligomers described above are excellent in compatibility with cellulose esters, and the transmittance when formed into a preferable film is 80% or more, more preferably 90% or more, and more preferably 92% or more. preferable.
  • the purpose of mixing at least one of polymer materials and oligomers other than cellulose ester includes meanings for controlling viscosity during heat melting and improving film physical properties after film processing. In this case, it can be included as the above-mentioned other additives.
  • fine particles such as a matting agent can be added in order to impart slipperiness
  • the fine particles include inorganic compound fine particles and organic compound fine particles.
  • the fine particles in which the matting agent is preferably as fine as possible are, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, strength, talc, calcined calcium hydrate, and calcium hydrate hydrate.
  • Inorganic fine particles such as aluminum silicate, magnesium silicate and calcium phosphate, and crosslinked polymer fine particles can be mentioned.
  • nickel carbonate is preferable because it can reduce the haze of the film.
  • fine particles such as silicon dioxide are surface-treated with an organic material, but such particles are preferred because they can reduce the haze of the film.
  • Preferred organic materials for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like.
  • the average particle size of the secondary particles of the fine particles is in the range of 0.05 to 1.0 m.
  • the average particle size of the secondary particles of the fine particles is preferably 5 to 50 nm, more preferably 7 to 14 nm.
  • these fine particles are preferably used in order to produce unevenness of 0.01 to 1. O / zm on the surface of the cellulose ester film.
  • the content of fine particles in cellulose ester is 0. respect cellulose ester 005 to 0.3 mass 0/0 are preferred.
  • Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, 0X50, TT600, etc. manufactured by Nippon Aerosil Co., Ltd. Aerogenole 200V, R972, R972V, R974, R202, R812 are preferable. Two or more of these fine particles may be used in combination. When two or more types are used together, they can be mixed and used at an arbitrary ratio. In this case, fine particles having different average particle diameters and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
  • the presence of fine particles in the film used as the matting agent can also be used to improve the strength of the film for another purpose.
  • the presence of the fine particles in the film can improve the orientation of the cellulose ester itself constituting the optical film of the present invention.
  • the optical film of the present invention is characterized by being formed by a melt casting method.
  • the molding method based on melt casting in which the solvent used in the solution casting method (for example, methylene chloride, etc.) is melted by heating is more specifically described in the melt extrusion molding method, press molding method, inflation method.
  • the injection molding method, the blow molding method and the stretch molding method can be classified. Among these, in order to obtain a polarizing plate protective film having excellent mechanical strength and surface accuracy, the melt extrusion method is excellent.
  • the winding length of the optical film of the present invention is preferably 500 to 5000 m, more preferably 1000 to 5 OOOm. It is also preferable to roll up with a knurling of 0 to 25% of the film thickness at both ends of the width.
  • volatile components such as moisture and impurities are removed before film formation or before melting.
  • This removal can be performed by a drying method, such as a heating method, a reduced pressure method, or a heated reduced pressure method. Drying may be performed in air or in an atmosphere where an inert gas such as nitrogen or argon is selected as the inert gas.
  • These inert gases preferably have a low water or oxygen content. It is preferable that the oxygen concentration is 0.1% or less, and the dew point of the gas is preferably 30 ° C or less. Most preferably, it does not contain substantially.
  • the moisture or impurities remaining after the removal in the drying step is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total mass of the film constituent materials. It is to make.
  • the cellulose ester is preferably used as 0.1 to: LOOOppm after further heat treatment to reduce moisture.
  • the amount of residual organic impurities can be measured by a headspace gas chromatography method. That is, a known amount of cellulose ester film is heated in a sealed container at 120 ° C. for 20 minutes, and the organic solvent contained in the gas phase in the sealed container is quantified by gas chromatography. From this result, the amount of residual organic solvent (%) can be calculated.
  • the film constituent materials can reduce the generation of volatile components by drying before film formation, and can be reduced by at least one type of resin other than the resin or the resin and the film constituent material. It can be divided into a mixture or a compatible material and dried.
  • the drying temperature is 80 ° C. or higher and is not higher than the Tg or melting point of the material to be dried. Including the viewpoint of avoiding the fusion between materials, the drying temperature, Yori at preferably 100-8 -5), and more preferably 110 ⁇ (Tg- 20) ° C.
  • the preferred drying time is 0.5 to 24 hours, more preferably 1 to 18 hours, and even more preferably 1.5 to 12 hours.
  • volatile component removal rate may be low, or drying may take too much time, and when Tg is present in the material to be dried, heating to a drying temperature higher than Tg causes the material to fuse. Handling may be difficult. It is preferable to perform the drying at 1 atm or less. It is particularly preferable to perform the drying while reducing the pressure from vacuum to 1 Z2 atm. Drying is preferably carried out with moderate agitation of materials such as fat, etc.
  • the fluidized bed method in which drying air or dry nitrogen is fed from the bottom in a drying container, performs the necessary drying in a shorter time. It is preferable because it is possible.
  • the drying process may be separated into two or more stages.
  • the material is stored using the preliminary drying process, and the film is formed by using the material that has been dried immediately before the film formation to 1 week before. It's okay.
  • the film-forming material After removing volatile components such as moisture and impurities in the film-forming material by a drying process, the film-forming material is individually or previously mixed Z pelletized and sent to a heated barrel. After being melted and fluidized, it is extruded into a sheet by a T-die.For example, it is brought into close contact with a cooling drum or an endless belt by an electrostatic application method or the like, cooled and solidified into a sheet, and an unstretched sheet is obtain. These processes are called casting processes
  • the melting temperature (temperature in the barrel) is preferably in the range of 150 to 250 ° C, more preferably in the range of 180 ° C to 230 ° C. More preferably, it is 190 ° C to 220 ° C.
  • the temperature of the cooling drum is preferably maintained at 90 to 150 ° C. If the drum temperature is 90 ° C or less, the die force extruded sheet will be cooled rapidly, and the structure in the film may become uneven in the film thickness direction, and may become brittle. The above is preferable. On the other hand, when the temperature is 150 ° C. or higher, the cooling rate of the unstretched sheet is decreased, which is preferable because productivity decreases.
  • the thickness of the protective film is preferably 10 to 500 ⁇ m! In particular, 10 to: LOO ⁇ m force ⁇ preferably, 20 to 80 ⁇ m force ⁇ preferable, particularly preferably 30 to 60 / ⁇ ⁇ .
  • the optical film is thicker than the above region, for example, when used as a polarizing plate protective film, the polarizing plate after polarizing plate processing becomes too thick, especially in the liquid crystal display used for notebook type Bazokon mopile type electronic devices. Thin and lightweight Not suitable for purpose.
  • the drying (solvent removal) load increases remarkably.
  • a drying (solvent removal) step is not required, so a film with a large film thickness is used. It can be manufactured with high productivity. Therefore, there is an advantage that it is easier than ever to increase the thickness of the film in accordance with the purpose such as imparting a necessary retardation or reducing moisture permeability.
  • even a thin film can be produced with high productivity by stretching such a thick film.
  • the film thickness of the stretched film becomes thin in inverse proportion to the draw ratio. For example, if the unstretched sheet is 200 ⁇ , stretching 100 times will yield 100 films.
  • the film thickness variation of the optical film support is ⁇ 3%, more preferably ⁇ 1%, more preferably ⁇ 0.
  • a range of 1% is preferable. These film thickness fluctuations can be reduced by stretching.
  • the width of the polarizing plate protective film is preferably lm or more.
  • the width of the optical film of the present invention is preferably from 1 to 4 m, particularly preferably from 1.4 to 2 m. Since it is difficult to uniformly extrude cellulose ester that has flowed from the barrel from the die to a width of 1.4 m or more, a film having a width of 1.4 m or more must be obtained unless it is laterally stretched. It is difficult.
  • the stretching process in this stretching process can also be employed for the stretching process in the case of water treatment.
  • the optical film using the cellulose ester of the present invention can lower the melting temperature and suppress the decrease in the molecular weight of the cellulose ester after melt extrusion. Can be manufactured at high speed. In addition, since the viscosity at the time of dissolution is low, a film with good flatness can be obtained even if the force is not stretched, and furthermore, since it can be stretched at a high magnification, an optical film with better flatness can be obtained. . Furthermore optical film Can be manufactured with high productivity.
  • the refractive index of cellulose ester increases in the stretched direction, and a slow axis is formed. Therefore, the stretch ratio is determined within the range of optical characteristics to be satisfied by the finally obtained film.
  • biaxial stretching is preferred. By stretching at the same magnification in the direction perpendicular to the first stretching axis, the occurrence of birefringence due to the first stretching is canceled, and an isotropic film can be obtained.
  • the ratio of the first stretching and the second stretching is changed, and the stretching ratio of either one is changed.
  • An optically anisotropic film can be obtained by stretching so as to be larger than the other stretching ratio.
  • the draw ratio between the width direction and the longitudinal direction is preferably 1.1 to 2.0, more preferably 1.2 to 1.5.
  • the film When stretching a plurality of times, the film may be stretched from the longitudinal direction or from the width direction. However, after the stretching process in the width direction, the conveyance width of the film is large. In order to increase the size of the transport device, it is preferable to perform stretching in the width direction after stretching in the longitudinal direction.
  • the final draw ratio of the optical film is preferably 1.5 to 4.0 times. 1. If it is less than 5 times, the obtained film may have poor flatness. On the other hand, stretching more than 4.0 times is difficult even when the cellulose ester of the present invention is used, and it is not preferable because there is a high possibility of breakage during the stretching process. More preferably, it is stretched 2.0 to 3.0 times.
  • the Tg of the optical film can be controlled by the type of material constituting the film and the ratio of the constituting materials.
  • the Tg when the film is dried is preferably 110 ° C or more, more preferably 120 ° C or more. This is because when the optical film of the present invention is used in a liquid crystal display device, if the Tg of the film is lower than the above, the temperature of the use environment, the humidity, and the influence of the heat of the knocklight cause the molecules fixed inside the film. The orientation state is affected, and there is a high possibility that the retardation value and the dimensional stability and shape of the film will be greatly changed. In addition, the shape of the film may not be maintained.
  • the glass transition temperature is preferably 180 ° C or lower, more preferably 150 ° C or lower. At this time, it can be obtained by the method described in Tgi IS K7121 of the film.
  • TD stretching it is preferable to perform transverse stretching while sequentially raising the temperature difference in the range of 1 to 50 ° C in a stretching region divided into two or more because the distribution of physical properties in the width direction can be reduced. Furthermore, after transverse stretching, holding the film within the range of Tg—40 ° C or more below the final TD stretching temperature for 0.01 to 5 minutes is preferable because the distribution of physical properties in the width direction can be further reduced.
  • Heat setting is usually performed at a temperature higher than the final TD stretching temperature and within a temperature range of Tg—20 ° C or lower, usually for 0.5 to 300 seconds. At this time, it is preferable to heat-set while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more.
  • the heat-set film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the transverse direction and the Z or longitudinal direction within a temperature range not higher than the final heat setting temperature and Tg or higher.
  • cooling is performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C or less per second.
  • Means for cooling and relaxation treatment are not particularly limited, and can be performed by conventionally known means. In particular, it is preferable to carry out these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film.
  • the cooling rate is a value obtained by (Ti-Tg) Zt, where Tl is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
  • the in-plane retardation value (Ro) and the retardation value in the thickness direction (Rth) of the optical film according to the present invention are 0 ⁇ Ro and Rth ⁇ 70 nm when used as a polarizing plate protective film. I prefer to be there! More preferably, 0 ⁇ Ro ⁇ 20nm, 0 ⁇ Rth ⁇ 50nm, more preferably 0 ⁇ Ro ⁇ 10nm and 0 ⁇ Rth ⁇ 30nm. When using as a retardation film, 30 ⁇ Ro ⁇ 100mn, 70 ⁇ Rth ⁇ 400mn, more preferably 35 ⁇ Ro ⁇ 65nn ⁇ 90 ⁇ Rth ⁇ 180nn efc5. In addition, it is preferable that the width of Rth fluctuation and distribution is less than ⁇ 10%, more preferably less than ⁇ 5%. More preferably, it is preferably less than ⁇ 1%, and most preferably, there is no fluctuation of Rth.
  • d is the thickness of the film (nm)
  • refractive index nx the maximum refractive index in the plane of the film, also referred to as the refractive index in the slow axis direction
  • ny in the film plane, the direction perpendicular to the slow axis
  • Nz reffractive index of the film in the thickness direction
  • the retardation values (Ro) and (Rth) can be measured using an automatic birefringence meter.
  • KOBRA-21ADH Oji Scientific Instruments
  • 23 ° C, 55% RH Can be obtained at a wavelength of 590 nm.
  • the slow axis is preferably in the width direction ⁇ 1 ° of the film or in the longitudinal direction ⁇ 1 °. More preferably, it is ⁇ 0.7 ° with respect to the width direction or the longitudinal direction, and further preferably ⁇ 0.5 ° with respect to the width direction or the longitudinal direction. By setting this range, the contrast of the obtained liquid crystal display can be increased.
  • the stretching treatment in the stretching step can also be employed in the stretching treatment in water treatment.
  • the optical film of the present invention does not substantially use a solvent in the film forming process, the amount of residual organic solvent contained in the optical film wound up after film formation is stably 0.1% by mass. Therefore, it is possible to provide an optical film having more stable flatness and Rth than before. In particular, it is possible to provide an optical film having stable flatness and Rth even for a long roll of 100 m or more.
  • the optical film can be used for any length of 1500m, 2500m, or 5000m, regardless of the winding length.
  • the clip gripping portions at both ends of the cut film are pulverized or granulated as necessary, and then used as film raw materials of the same type. Or you may reuse as a raw material for films of a different kind.
  • functions such as antistatic layer, hard coat layer, antireflection layer, slippery layer, easy adhesion layer, antiglare layer, barrier layer, and optical compensation layer before and after stretching and after Z A sex layer may be applied.
  • various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment are performed as necessary. Can be applied.
  • a cellulose ester film having a laminated structure can be produced by co-extrusion of a composition containing cellulose resin having different additive concentrations such as the plasticizer, ultraviolet absorber, and matting agent.
  • a cellulose ester film having a structure of skin layer / core layer Z skin layer can be produced.
  • the matting agent can be included in the skin layer more or only in the skin layer.
  • More plasticizers and UV absorbers can be contained in the core layer than in the skin layer, and may be contained only in the core layer. It is also possible to change the types of plasticizers and ultraviolet absorbers in the core layer and skin layer.
  • the Tg of the core layer is preferably lower than the Tg of the skin layer, which may be different even if the Tg of the skin layer and the core layer are different. Also, the viscosity of the melt containing the cellulose ester during melt casting may be different between the skin layer and the core layer. The viscosity of the skin layer may be greater than the viscosity of the core layer, or the viscosity of the core layer may be equal to or greater than the viscosity of the skin layer. .
  • the method for producing a polarizing plate using the optical film of the present invention is not particularly limited, and can be produced by a general method.
  • the optical film of the present invention is obtained by using a completely poly (polybulal alcohol) aqueous solution on at least one surface of a polarizer prepared by subjecting the obtained optical film to an alkali treatment and immersing and stretching a polyvinyl alcohol film in an iodine solution. Paste.
  • the optical film of the present invention may be bonded to both sides of the polarizer as a polarizing plate protective film.
  • polarizing plate processing may be performed by performing such easy adhesion processing.
  • the polarizing plate is composed of a polarizer and protective films for protecting both sides of the polarizer. Further, a protective film is bonded to one surface of the polarizing plate, and a separate film is bonded to the other surface. Can be achieved.
  • the protective film and separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protective film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate.
  • the separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the surface side of the polarizing plate to be bonded to the liquid crystal cell.
  • a substrate containing liquid crystal is usually disposed between two polarizing plates.
  • a polarizing plate protective film to which the optical film of the present invention is applied has high flatness and uniformity of retardation. Excellent display properties can be obtained even if it is placed on the site.
  • a polarizing plate protective film provided with a clear hard coat layer, an antiglare layer, an antireflective layer, or the like is preferably used for the polarizing plate protective film on the display side outermost surface of the liquid crystal display device.
  • a polarizing plate protective film provided with an optical compensation layer or a polarizing plate protective film provided with appropriate optical compensation ability by itself, such as stretching operation, it can be disposed at a site in contact with the liquid crystal cell. Excellent display properties can be obtained.
  • the effect of the present invention can be further exerted by using it in a multi-domain liquid crystal display device, more preferably in a multi-domain liquid crystal display device by a birefringence mode.
  • the multi-domain method is a method of dividing the liquid crystal cell that constitutes one pixel into a plurality of parts. It is suitable for improving the viewing angle dependency and improving the symmetry of image display. “Okita, Yamauchi: Liquid Crystal, 6 (3), 303 (2002)”. The liquid crystal display cell is also shown in “Yamada, Hyundaira: Liquid Crystal, 7 (2), 184 (2003)”, but is not limited thereto.
  • the display quality of the display cell is preferably symmetrical in human observation. Therefore, when the display cell is a liquid crystal display cell, the domain can be multiplied substantially giving priority to the symmetry on the observation side.
  • a known method can be used to divide the domain, and can be determined by a two-division method, more preferably a four-division method in consideration of the properties of the known liquid crystal mode.
  • the polarizing plate of the present invention is a multi-domestic vertical alignment (MVA) mode typified by a vertical alignment mode, in particular, an MVA mode divided into four, and a multi-domain by electrode arrangement. It can be effectively used in the well-known main PVA (Patterned Vertical Alignment) mode and the CPA (Continuous Pinwheel Alignment) mode, which combines electrode arrangement and chirality.
  • MVA Manufacturing Vertical Alignment
  • CPA Continuous Pinwheel Alignment
  • a proposal of an optically biaxial film is also disclosed in conformity with the OCB (Optical Compensated Bend) mode, and “T. Miya shita, T. Uchida: J.
  • the effect of the present invention can be exhibited in the display quality by the polarizing plate of the present invention. If the effect of the present invention can be exhibited by using the polarizing plate of the present invention, the arrangement of the liquid crystal mode and the polarizing plate is not limited.
  • the liquid crystal display device has high performance as a device for colorization and moving image display, the display quality of the liquid crystal display device using the optical film of the present invention, particularly a large liquid crystal display device, is less fatigued and faithful. Display of moving images is possible.
  • Cellulose acetate propionate 1 (weight average molecular weight; 200,000, acetyl substitution degree; 1.95, propyl substitution degree; 0.75)
  • Water solubility Polyethylene glycol (number average molecular weight 600) lOOOg Hydrophobicity: Trimethylolpropane tribenzoate (Asahi Denka Kogyo Co., Ltd.) 500g TINUVIN144 (Chinoku's Specialty Chemicals Co., Ltd.) 400g
  • UV absorber LA-31 (Asahi Denka Kogyo Co., Ltd.) 100g R972V (Enomoto Aerosil Co., Ltd.) 50g
  • composition 1 was stirred with a Henschel mixer at 3000 rpm for 3 minutes, and the additive was dispersed and mixed with cellulose. A part (20-30 g) of the obtained mixture was set aside for melting point and melt viscosity measurement. While pulling the vacuum pump with a vacuum dryer (yamato DP41), the resulting mixture was discharged from the purge port with a dew point of -40 ° C N gas.
  • the moisture content of the molded product after drying was 120 ppm when measured by a coulometric titration method using a Karl Fischer moisture measuring device (manufactured by Dia Instruments MEN: CA-06, VA-06).
  • Scratch removal condition Scratch removal, roller dip, and roller peripheral speed can be adjusted with a single scraper. And made a 100 ⁇ m film.
  • the average film thickness d In accordance with the method described above, measure 10 locations in the width direction of the sample (3 times Z locations), and calculate the maximum value and the letter value R (average value of 3 times measurement) at each location.
  • the AR force is nm or less, it is easy to see on the image display device without color misalignment or unevenness.
  • a display image is obtained.
  • a cellulose acylate film is placed between two polarizing plates (crossed Nicols state) that are stacked so that their absorption axes are perpendicular to each other, and the surface irregularity of the film is visually observed. Flatness was evaluated. Poor flatness! Some things are weak! Light leaks and is observed as surface irregularities.
  • Table 2 shows the results of the plasticizer. Samples listed in Table 2 13
  • a 120 ⁇ m-thick polybulal alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). Immerse this in an aqueous solution of 0.075g of iodine, 5g of potassium yowi, and water lOOg for 60 seconds, then soak in an aqueous solution of 68 ° C that also has 6g of potassium iodide, 7.5g of boric acid, and water lOOg. did. This was washed with water and dried to obtain a polarizer.
  • Step 1 The optical film in which the side to be bonded to the polarizer is dipped is immersed in a 2 mol / L sodium hydroxide solution at 60 ° C for 90 seconds, then washed with water and dried. Obtained.
  • Step 2 The polarizer was immersed in a polybulal alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 3 Excess adhesive adhered to the polarizer in Step 2 was gently wiped, and this was placed on each optical film processed in Step 1 and laminated.
  • Step 4 The optical film and the polarizer laminated in Step 3 were bonded at a pressure of 20 to 30 NZcm 2 and a conveying speed of about 2 mZ.
  • Step 5 A sample obtained by bonding the optical film prepared in Step 4 and the polarizer in a drier at 80 ° C was dried for 2 minutes to prepare a polarizing plate.
  • a liquid crystal panel for visibility evaluation was prepared as follows, and the characteristics as a polarizing plate and a liquid crystal display device were evaluated.
  • the polarizing plate previously bonded to the liquid crystal television is peeled off, and the above-prepared polarizing plate is bonded to the glass surface of the liquid crystal cell. did.
  • the two polarizing plates thus prepared were stuck so as to be orthogonal to each other so that the polarization axis of the polarizing plate was not changed from the original, and the polarizing plate, the liquid crystal display device, and the like.
  • the polarizing plate and liquid crystal display device using the optical film of the present invention are superior in contrast to the polarizing plate and liquid crystal display device using the optical film of Comparative Example 1. Showed sex.

Abstract

Disclosed is an optical film excellent in planarity and optical characteristics, which is produced by heating and melting a melt containing a cellulose ester resin and a plasticizer. Also disclosed are a method and apparatus for producing such an optical film, a polarizing plate and a liquid crystal display. Specifically disclosed is a method for producing an optical film wherein at least a cellulose ester resin and a plasticizer are heated and melted to be formed into a film by flow casting. This method for producing an optical film is characterized in that the film formed by flow casting is treated with water.

Description

明 細 書  Specification
光学フィルム、その製造方法およびその製造装置、並びに偏光板、液晶 表示装置  OPTICAL FILM, MANUFACTURING METHOD THEREOF, ITS MANUFACTURING DEVICE, POLARIZING PLATE, LIQUID CRYSTAL DISPLAY DEVICE
技術分野  Technical field
[0001] 本発明は、光学フィルム、その製造方法及びその製造装置、並びに偏光板、液晶 表示装置に関し、より詳しくはセルロースエステル榭脂、可塑剤を含む溶融物を加熱 溶融して製造した、平面性及び光学特性に優れる光学フィルム、その製造方法及び その製造装置、並びに偏光板、液晶表示装置に関する。  TECHNICAL FIELD [0001] The present invention relates to an optical film, a production method thereof, a production apparatus thereof, a polarizing plate, and a liquid crystal display device, and more specifically, a flat surface produced by heating and melting a melt containing cellulose ester resin and a plasticizer. The present invention relates to an optical film having excellent properties and optical properties, a production method thereof, a production apparatus thereof, a polarizing plate, and a liquid crystal display device.
背景技術  Background art
[0002] 一般に、光学フィルムは、液晶ディスプレイの偏光板の保護フィルム、反射防止層、 防眩層、ハードコート層を設けて、液晶ディスプレイやプラズマディスプレイ等の最表 面に使用されている。  In general, an optical film is provided on the outermost surface of a liquid crystal display or a plasma display by providing a protective film for a polarizing plate of a liquid crystal display, an antireflection layer, an antiglare layer, and a hard coat layer.
[0003] 光学フィルムは、高 、透明性、平面性、透湿防止性、ブリードアウト耐性、寸法安定 性 (温湿度や経時で変動しない）、偏光板に使用される PVA偏光膜との密着性、な どの各種性能が要求されている。光学用のセルロースエステルフィルムは、特に偏光 板に使用される PVA偏光膜との密着性と適度な透湿防止性から、偏光板保護フィム ルとして使用されている力 セルロースエステルフィルムは、一般にハロゲン系有機 溶剤を使用した溶液流延製膜法によって製造されている。しかしながら、ハロゲン系 有機溶剤は、環境面、安全面力 その使用が制限されつつある。  [0003] Optical films have high transparency, flatness, moisture permeation prevention, bleed-out resistance, dimensional stability (does not vary with temperature and humidity and time), and adhesion to PVA polarizing films used for polarizing plates. Various performances are required. Cellulose ester films for optical use are generally used as polarizing plate protective films because of their adhesion to PVA polarizing films used in polarizing plates and appropriate moisture permeation prevention properties. Manufactured by a solution casting method using an organic solvent. However, the use of halogenated organic solvents is being restricted in terms of environmental and safety aspects.
[0004] このため、有機溶剤を使用しな 、セルロースエステルフィルムの製造方法が求めら れており、溶融流延法などの加熱溶融によりフィルムを得る方法が提案されている（ 例えば、特許文献 1、 2参照。；)。しかし、セルロースエステル榭脂は、一般的に熱によ り劣化しやすい材料のため、上記の光学フィルムに求められる諸性能を完全に満足 できていない。  [0004] For this reason, there is a demand for a method for producing a cellulose ester film without using an organic solvent, and a method for obtaining a film by heat melting such as a melt casting method has been proposed (for example, Patent Document 1). 2);). However, cellulose ester resin is generally a material that is easily deteriorated by heat, and thus does not completely satisfy the various properties required for the optical film.
[0005] 一方で、セルロースエステル榭脂を繊維として使用するために、溶融紡糸用の加熱 溶融させる技術として、ポリエーテルィ匕合物を可塑剤として 5〜20質量％含有させる ことで溶融紡糸性に優れ、強伸度特性のみならず繊度の均一性にも優れた繊維を 得る方法が提案されている (例えば、特許文献 3参照。 )0 [0005] On the other hand, in order to use cellulose ester resin as a fiber, it is excellent in melt spinnability by containing 5 to 20% by mass of a polyethery compound as a plasticizer as a technique for heating and melting for melt spinning. , Fibers with excellent elongation properties as well as fineness uniformity The method of obtaining has been proposed (e.g., see Patent Document 3.) 0
[0006] この技術をセルロースエステル系光学フィルムに適用することが考えられる力 本発 明者らの検討によれば、光学フィルムにおいては、溶融紡糸では課題とならない、平 面性および光学特性、特にロール状に成膜したフィルム幅手方向の位相差調整へ の対応が困難であることが分力つた。 [0006] Power that can be considered to apply this technology to cellulose ester-based optical films According to the study by the present inventors, the flatness and optical characteristics, particularly the optical films, which are not a problem in melt spinning, It was difficult to cope with the phase difference adjustment in the width direction of the film formed into a roll.
特許文献 1：特開 2000— 352620号公報  Patent Document 1: Japanese Patent Laid-Open No. 2000-352620
特許文献 2：特開 2005— 178194号公報  Patent Document 2: JP-A-2005-178194
特許文献 3 :特開 2004— 182979号公報  Patent Document 3: Japanese Patent Application Laid-Open No. 2004-182979
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 従って本発明の目的は、セルロースエステル榭脂、可塑剤を含む溶融物を加熱溶 融して製造した、平面性及び光学特性に優れる光学フィルム、その製造方法及びそ の製造装置、並びに偏光板、液晶表示装置を提供することにある。 [0007] Therefore, an object of the present invention is to produce an optical film excellent in flatness and optical properties, produced by heat-melting a melt containing cellulose ester resin and a plasticizer, a production method thereof, an apparatus for producing the same, and The object is to provide a polarizing plate and a liquid crystal display device.
課題を解決するための手段  Means for solving the problem
[0008] 本発明の上記目的は、下記構成により達成された。 [0008] The above object of the present invention has been achieved by the following constitution.
少なくともセルロースエステル榭脂及び可塑剤を加熱溶融させてフィルム状に流延 製膜する光学フィルムの製造方法において、フィルム状に流延製膜した後、水処理 することを特徴とする光学フィルムの製造方法。  In the method for producing an optical film in which at least cellulose ester resin and a plasticizer are melted by heating and cast into a film, the film is cast into a film and then water-treated. Method.
[0009] 2.前記水処理時にフィルムを幅保持または延伸処理することを特徴とする前記 1 記載の光学フィルムの製造方法。 [0009] 2. The method for producing an optical film as described in 1 above, wherein the width of the film is maintained or stretched during the water treatment.
[0010] 3.前記水処理を、 1槽以上の水槽内で行うものであることを特徴とする前記 1また は 2記載の光学フィルムの製造方法。 [0010] 3. The method for producing an optical film as described in 1 or 2 above, wherein the water treatment is performed in one or more water tanks.
[0011] 4.前記可塑剤として水溶性可塑剤を使用することを特徴とする前記 1〜3いずれか の項記載の光学フィルムの製造方法。 [0011] 4. The method for producing an optical film as described in any one of 1 to 3 above, wherein a water-soluble plasticizer is used as the plasticizer.
[0012] 5.前記可塑剤として水溶性可塑剤および疎水性可塑剤を使用することを特徴とす る前記 1〜4いずれかの項記載の光学フィルムの製造方法。 [0012] 5. The method for producing an optical film as described in any one of 1 to 4 above, wherein a water-soluble plasticizer and a hydrophobic plasticizer are used as the plasticizer.
[0013] 6.前記 1〜5いずれかの項記載の光学フィルムの製造方法で得られることを特徴と する光学フィルム。 [0014] 7.前記 6記載の光学フィルムを、偏光子を挟む 2枚の偏光板保護フィルムのうち少 なくとも一枚として用いたことを特徴とする偏光板。 [0013] 6. An optical film obtained by the method for producing an optical film as described in any one of 1 to 5 above. [0014] 7. A polarizing plate, wherein the optical film described in 6 is used as at least one of two polarizing plate protective films sandwiching a polarizer.
[0015] 8.前記 7記載の偏光板を用いたことを特徴とする液晶表示装置。 [0015] 8. A liquid crystal display device using the polarizing plate described in 7 above.
[0016] 9.少なくともセルロースエステル榭脂および可塑剤を加熱溶融させてフィルム状に 流延製膜する光学フィルムの製造装置において、少なくともフィルム状に流涎製膜す る工程、水処理工程および卷取り工程を有することを特徴とする光学フィルムの製造 装置。 [0016] 9. In an optical film manufacturing apparatus in which at least a cellulose ester resin and a plasticizer are heated and melted and cast into a film, a process for forming a film into a film at least, a water treatment process, and wrinkling are performed. An optical film manufacturing apparatus comprising a step.
発明の効果  The invention's effect
[0017] 本発明により、セルロースエステル榭脂、可塑剤を含む溶融物を加熱溶融して製造 した、平面性及び光学特性に優れる光学フィルム、その製造方法及びその製造装置 、並びに偏光板、液晶表示装置を提供することが出来る。  [0017] According to the present invention, an optical film produced by heating and melting a melt containing cellulose ester resin and a plasticizer, having excellent flatness and optical properties, a production method and production apparatus thereof, a polarizing plate, and a liquid crystal display A device can be provided.
図面の簡単な説明  Brief Description of Drawings
[0018] [図 1]本発明に係わる製造装置の断面図である。 FIG. 1 is a cross-sectional view of a manufacturing apparatus according to the present invention.
符号の説明  Explanation of symbols
[0019] 1 押出し機 [0019] 1 Extruder
2 フィルター  2 Filter
3 スタチックミキサー  3 Static mixer
4 流延ダイ  4 Casting die
11 第 1冷却ドラム  11 First cooling drum
12 第 2冷却ドラム  12 Second cooling drum
13 第 3冷却ドラム  13 Third cooling drum
14 剥離ロール  14 Peeling roll
15 ダンサーローノレ  15 Dancer Ronore
16 延伸機  16 Stretching machine
17 スリツター  17 slitter
18 エンボスリング  18 Embossing ring
19 ノ ックローノレ  19 Noc Ronore
20 卷取り機 30 水中テンター 20 Dredge machine 30 Underwater tenter
31 水槽  31 aquarium
32 乾燥機  32 dryer
F 巻き取られた光学フィルム  F Wound optical film
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0020] 以下本発明を実施するための最良の形態について詳細に説明する力 本発明はこ れらに限定されるものではない。 [0020] The following is a detailed explanation of the best mode for carrying out the present invention. The present invention is not limited to these.
[0021] 本発明の光学フィルムは、少なくともセルロースエステル榭脂及び可塑剤を加熱溶 融させてフィルム状に流延製膜する光学フィルムの製造方法にぉ 、て、フィルム状に 流延製膜した後、水処理することを特徴とする。 [0021] The optical film of the present invention was cast into a film shape according to a method for producing an optical film in which at least cellulose ester resin and a plasticizer were melted by heating and cast into a film shape. After that, it is characterized by water treatment.
[0022] 本発明にお 、て、水処理とは、流延製膜してロール状のフィルムとしたものを、巻き 取るまでの間で、水を満たした水槽に所定の時間浸漬することを 、う。 In the present invention, water treatment refers to immersing a film formed by casting into a roll-shaped film in a water tank filled with water for a predetermined time until winding. Uh.
[0023] 水処理の水は、純水、蒸留水、イオン交換水、水道水等、通常工業的に使用できる ものをいずれも採用することができる。 [0023] As water for water treatment, pure water, distilled water, ion-exchanged water, tap water and the like which can be usually used industrially can be used.
[0024] 水処理に使用される水の温度は、室温以上 100°C以下であり、好ましくは、 50〜9[0024] The temperature of water used for water treatment is not less than room temperature and not more than 100 ° C, preferably 50-9.
8°Cを選択することができる。 8 ° C can be selected.
[0025] 水処理の時間は、フィルム膜厚等の諸条件にしたカ^、、適宜定めることができるが[0025] The water treatment time can be appropriately determined according to various conditions such as film thickness.
、 20〜120 /ζ πιのフィルムの場合、 1〜120分、好ましくは、 5〜70分の範囲で選択 することができる。 In the case of a film of 20 to 120 / ζ πι, it can be selected in the range of 1 to 120 minutes, preferably 5 to 70 minutes.
[0026] 水処理のための水槽は 1槽以上に分離させてもよい。 4槽以下であることが、工程 管理の点力 好ましい。複数の水槽を採用する場合、水槽の切り替わり箇所におい て、水切り処理をすることが好ましぐまた、水槽毎の水の混じりあいを避けるために、 別途シャワーによる水洗処理をしてもよい。最後の水槽を通過した後は、フィルムを 乾燥させることが好ましい。  [0026] The water tank for water treatment may be separated into one or more tanks. The point of process control is preferably 4 tanks or less. When multiple tanks are used, it is preferable to drain water at the place where the tanks are switched. In addition, in order to avoid mixing water in each tank, it may be separately washed with a shower. After passing through the last water tank, it is preferable to dry the film.
[0027] 水処理の水には、塩、界面活性剤、 ΡΗ調整剤、防腐剤等の添加剤を含有させても よぐ水の ΡΗは 1〜12の間で緩衝剤を添加することにより適宜選択することができる  [0027] Water for water treatment may contain additives such as salts, surfactants, wrinkle adjusters, preservatives, etc. Can be selected as appropriate
[0028] 水処理に使用する水は、使用時間を重ねることにより、フィルムの添加剤の染み出 しが発生し汚染されてくるが、汚染度を適宜測定し、新たな水に置き換えることができ る。また、循環浄ィ匕使用することも可能である。 [0028] The water used for water treatment oozes out additives in the film over time. It will be contaminated with water, but it is possible to measure the degree of contamination as appropriate and replace it with new water. It is also possible to use a circulation purifier.
[0029] 複数水槽が採用された場合、水槽毎に前記諸条件は、適宜選択することができる。  [0029] When a plurality of water tanks are employed, the various conditions can be appropriately selected for each water tank.
水槽の一部で、ケンィ匕処理をすることも可能である。  It is also possible to perform ken treatment in a part of the water tank.
[0030] 水処理するために水槽に浸漬されている間、フィルムは、テンター等によって、幅保 持されていることが好ましい。また、テンターによって延伸処理されることが好ましい。 延伸処理は、通常、位相差の調整のために使用される処理をそのまま採用すること ができる。 [0030] While being immersed in a water tank for water treatment, the film is preferably held in width by a tenter or the like. Moreover, it is preferable to carry out an extending | stretching process with a tenter. As the stretching process, a process usually used for adjusting the phase difference can be employed as it is.
[0031] 本発明における溶融流延とは、溶媒を用いずセルロースエステルを、流動性を示 す温度まで加熱溶融し、その後、流動性のセルロースエステルを流延することを溶融 流延として定義する。加熱溶融する成形法は更に詳細には溶融押出成形法、プレス 成形法、インフレーション法、射出成形法、ブロー成形法、延伸成形法などに分類で きる。これらの中で、機械的強度及び表面精度などに優れる光学フィルムを得るため には、溶融押出し法が優れている。ここでフィルム構成材料が加熱されて、その流動 性を発現させた後、ドラムまたはエンドレスベルト上に押出し製膜することが、溶融流 延製膜法として本発明のセルロースエステルフィルムの製造方法に含まれる。  [0031] Melt casting in the present invention is defined as melt casting in which a cellulose ester is heated and melted to a temperature exhibiting fluidity without using a solvent, and then the fluid cellulose ester is cast. . The molding method for heating and melting can be further classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretch molding method. Among these, the melt extrusion method is excellent for obtaining an optical film excellent in mechanical strength and surface accuracy. Here, after the film constituent material is heated to exhibit its fluidity, extrusion film formation on a drum or endless belt is included in the method for producing a cellulose ester film of the present invention as a melt casting film formation method. It is.
[0032] 本発明の可塑剤としては、水溶性可塑剤を使用するのが好ましい。水溶性可塑剤 とは、 25°Cでの lOOgの純水への溶解量が 5g以上のものをいう。好ましくは、 7g以上 である。  [0032] It is preferable to use a water-soluble plasticizer as the plasticizer of the present invention. A water-soluble plasticizer is one whose lOOg dissolved in pure water at 25 ° C is 5g or more. Preferably, it is 7 g or more.
[0033] 本発明の可塑剤としては、水溶性可塑剤に疎水性可塑剤を混合して用いることが 好ましい。疎水性可塑剤とは、 25°Cでの lOOgの純水への溶解量が 5g未満のものを いう。好ましくは、 3g以下である。  [0033] The plasticizer of the present invention is preferably used by mixing a hydrophobic plasticizer with a water-soluble plasticizer. Hydrophobic plasticizers are those whose lOOg dissolved in pure water at 25 ° C is less than 5 g. Preferably, it is 3 g or less.
[0034] 本発明に用いる可塑剤としては、通常偏光板用保護フィルムとして使用することが できる可塑剤を適宜採用することができる。例えばリン酸エステル誘導体、カルボン 酸エステル誘導体が好ましく用いられる。また、特開 2003— 12859号に記載の重量 平均分子量が 500以上 10000以下であるエチレン性不飽和モノマーを重合して得 られるポリマー、アクリル系ポリマー、芳香環を側鎖に有するアクリル系ポリマーまた はシクロへキシル基を側鎖に有するアクリル系ポリマーなども好ましく用いられる。 [0035] 本発明の可塑剤は、水溶性可塑剤と疎水性可塑剤とは、構造的に近似して!/ヽるも のであっても、水に対する溶解性が異なることによって、フィルムの平面性、光学特性 への寄与が大きくことなり、水溶性の相違をもって同じ系統の化合物力 適宜選択す ることがでさる。 [0034] As the plasticizer used in the present invention, a plasticizer that can be generally used as a protective film for a polarizing plate can be appropriately employed. For example, phosphoric acid ester derivatives and carboxylic acid ester derivatives are preferably used. In addition, a polymer obtained by polymerizing an ethylenically unsaturated monomer having a weight average molecular weight of 500 or more and 10,000 or less described in JP-A-2003-12859, an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, or An acrylic polymer having a cyclohexyl group in the side chain is also preferably used. [0035] Although the water-soluble plasticizer and the hydrophobic plasticizer of the plasticizer of the present invention are structurally similar! Therefore, the compound power of the same strain can be selected as appropriate depending on the difference in water solubility.
[0036] (可塑剤）  [0036] (Plasticizer)
(アルコール系化合物）  (Alcohol compounds)
本発明に用いられるアルコール系化合物は特に限定されるものではなぐ 1価〜多 価のアルコール系化合物を用いることが出来る。  The alcohol compound used in the present invention is not particularly limited, and monovalent to polyvalent alcohol compounds can be used.
[0037] 具体的には、 1価のアルコールとしては、ブチルアルコール、（iso—または n—)アミ ノレァノレコーノレ、へキシノレアノレコーノレ、ヘプチノレアノレコーノレ、 1ーォクタノーノレ、 2—ェ チルへキシルアルコール、 n—ドデシルアルコール、ラウリルアルコール、ォレイルァ ルコール等、 2価のアルコールとしては、 1, 5—ペンタジオール、エチレングリコール 、プロピレングリコール、 2メチル 2, 4ペンタジオール、 1, 6—へキサンジオール等、 3 価のアルコールとしては、トリメチロールプロパン、トリメチロールェタン、グリセリン、フ ィタントリオール等、 4価のアルコールとしては、ペンタエリスリトール、ジグリセリン等、 多価アルコールとしては、ポリグリセリンが挙げられる。  [0037] Specifically, the monohydric alcohols include butyl alcohol, (iso- or n-) aminoleanolone, hexinoreanoreconole, heptinoleanoreconole, 1-octanol, 2 — Diethyl alcohols such as ethylhexyl alcohol, n-dodecyl alcohol, lauryl alcohol, and oleyl alcohol include 1,5-pentadiol, ethylene glycol, propylene glycol, 2-methyl 2,4 pentadiol, 1, 6 -Trivalent alcohols such as hexanediol, trimethylolpropane, trimethylolethane, glycerin, phytanetriol, etc., tetravalent alcohols such as pentaerythritol, diglycerin, etc. Polyglycerin is mentioned.
[0038] これらの中で、炭素数が 7以上の 1価のアルコールが好ましい。更に沸点が 160°C 以上であることが好ましい。 Cの数が 7未満の場合、沸点、引火点が低ぐ沸点が 160 °Cより低いと、加熱成型時揮発が著しぐ工程汚染が問題となる。また引火点が 60°C 以下の物質は危険物の対象となり、消防法においても 4類第 2石油類以下 (特殊引 火物、 1石）となり、危険性が非常に高い。また、水溶性となる為ブリードアウト耐性が 劣化する。上記アルコール系化合物の中では、ヘプチルアルコール、 1ーォクタノー ル、 2—ェチルへキシルアルコール、 n—ドデシルアルコール、ラウリルアルコール、 ォレイルアルコール等が本発明の効果を得る上で好ましいアルコール系化合物であ る。  Of these, monovalent alcohols having 7 or more carbon atoms are preferred. Further, the boiling point is preferably 160 ° C or higher. When the number of C is less than 7, if the boiling point and flash point are low and the boiling point is lower than 160 ° C, process contamination with significant volatilization during heat molding becomes a problem. Substances with a flash point of 60 ° C or lower are also classified as dangerous goods, and they are classified as Class 4 No. 2 petroleums (special flammables, 1 stone) under the Fire Service Law and are extremely dangerous. In addition, bleed-out resistance deteriorates due to water solubility. Among the alcohol compounds, heptyl alcohol, 1-octanol, 2-ethylhexyl alcohol, n-dodecyl alcohol, lauryl alcohol, oleyl alcohol and the like are preferable alcohol compounds for obtaining the effects of the present invention. .
[0039] 多価アルコールの場合は、融点が 60°C以下でかつ、沸点が 160°C以上であること が好ましぐ融点は低いほど好ましい。融点が 70°Cを超えると融点低下効果、溶融粘 度低下効果は低くなる。また、沸点は 160°Cより低いと、加熱成型時、揮発が著しぐ 工程汚染が問題になる。 [0039] In the case of a polyhydric alcohol, it is preferable that the melting point is 60 ° C or lower and the boiling point is 160 ° C or higher. When the melting point exceeds 70 ° C, the melting point lowering effect and the melt viscosity lowering effect are reduced. Also, if the boiling point is lower than 160 ° C, volatilization will be significant during heat molding. Process contamination becomes a problem.
[0040] リン酸エステル誘導体としては、例えば、可塑剤としては、リン酸エステル系可塑剤 、エチレングリコールエステル系可塑剤、グリセリンエステル系可塑剤、ジグリセリンェ ステル系可塑剤（脂肪酸エステル）、多価アルコールエステル系可塑剤、ジカルボン 酸エステル系可塑剤、多価カルボン酸エステル系可塑剤、ポリマー可塑剤等が挙げ られる。この中でも多価アルコールエステル系可塑剤、ジカルボン酸エステル系可塑 剤及び多価カルボン酸エステル系可塑剤が好ましい。また、可塑剤は液体であって も固体であっても良ぐ組成物の制約上無色であることが好ましい。熱的にはより高温 において安定であることが好ましぐ分解開始温度が 150°C以上、更に 200°C以上 が好ましい。添加量は前記の光学フィルムに求められる諸性能の為に調整出来、そ の配合量は、本発明の目的を損なわない範囲で適宜選択され、セルロースエステル 榭脂 100質量部に対して好ましくは 1〜50質量％、より好ましくは 3〜30質量％であ る。特に 5〜15質量％が好ましい。  [0040] Examples of the phosphoric acid ester derivative include a phosphoric acid ester plasticizer, an ethylene glycol ester plasticizer, a glycerin ester plasticizer, a diglycerin ester plasticizer (fatty acid ester), and a polyhydric alcohol. Examples thereof include ester plasticizers, dicarboxylic acid ester plasticizers, polycarboxylic acid ester plasticizers, and polymer plasticizers. Of these, polyhydric alcohol ester plasticizers, dicarboxylic acid ester plasticizers, and polycarboxylic acid ester plasticizers are preferred. In addition, the plasticizer may be liquid or solid, and it is preferable that the plasticizer is colorless because of restrictions on the composition. Thermally, the decomposition initiation temperature is preferably 150 ° C or higher, more preferably 200 ° C or higher, which is preferably stable at higher temperatures. The addition amount can be adjusted for various performances required for the optical film, and the blending amount thereof is appropriately selected within the range not impairing the object of the present invention, and is preferably 1 with respect to 100 parts by mass of the cellulose ester resin. -50 mass%, more preferably 3-30 mass%. 5 to 15% by mass is particularly preferable.
[0041] 以下、本発明に用いられる可塑剤について更に説明する。具体例はこれらに限定 されるものではない。 [0041] Hereinafter, the plasticizer used in the present invention will be further described. Specific examples are not limited to these examples.
[0042] リン酸エステル系の可塑剤：具体的には、トリァセチルホスフェート、トリブチルホス フェート等のリン酸アルキルエステル、トリシクロベンチルホスフェート、シクロへキシル ホスフェート等のリン酸シクロアルキルエステル、トリフエ-ルホスフェート、トリクレジル ホスフェート、クレジノレフエ-ノレホスフェート、オタチノレジフエ-ノレホスフェート、ジフエ 二ルビフエ二ノレホスフェート、トリオクチノレホスフェート、トリブチノレホスフェート、トリナ フチルホスフェート、トリキシリルォスフェート、トリスオルト一ビフエ-ルホスフェート等 のリン酸ァリールエステルが挙げられる。これらの置換基は、同一でもあっても異なつ ていてもよく、更に置換されていても良い。またアルキル基、シクロアルキル基、ァリー ル基のミックスでも良く、また置換基同志が共有結合で結合して 、ても良 、。  [0042] Phosphoric ester plasticizers: specifically, phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate, and triphenyl- Ruphosphate, tricresyl phosphate, credinole-nore phosphate, otachinoresphie-nore phosphate, diphenol dirubibinenophosphate, trioctinorephosphate, tribubutinorephosphate, trinaphthyl phosphate, trixylyl phosphate, trisorthophosphate And phosphoric acid aryl ester. These substituents may be the same or different, and may be further substituted. Also, it may be a mix of alkyl, cycloalkyl, and aryl groups, and the substituents may be covalently bonded.
[0043] またエチレンビス（ジメチルホスフェート）、ブチレンビス（ジェチルホスフェート）等の ァノレキレンビス（ジァノレキノレホスフェート）、エチレンビス（ジフエ-ノレホスフェート）、プ ロピレンビス（ジナフチノレホスフェート）等のァノレキレンビス（ジァリーノレホスフェート）、 フエ-レンビス（ジブチノレホスフェート）、ビフエ-レンビス（ジ才クチノレホスフェート）等 のァリーレンビス（ジァノレキノレホスフェート;)、フエ二レンビス（ジフエ二ノレホスフェート；） 、ナフチレンビス（ジトルィルホスフェート）等のァリーレンビス（ジァリールホスフェート )等のリン酸エステルが挙げられる。これらの置換基は、同一でもあっても異なってい てもよく、更に置換されていても良い。またアルキル基、シクロアルキル基、ァリール 基のミックスでも良く、また置換基同志が共有結合で結合して 、ても良!、。 [0043] In addition, ananolene bis (ethylene bis (dimethyl phosphate), butanolene bis (diethyl quinolephosphate), ethylene bis (diphenol-phosphate phosphate), propylene bis (dinaphthinorephosphate), etc. Diarynophosphate), Huerlenbis (Dibutinorephosphate), Bi-Lenbis (Di-Cutinorephosphate), etc. And phosphate esters such as arylene bis (diaryl phosphate) such as arylene bis (diolequinophosphate;), phenylene bis (diphenyl phosphate), and naphthylene bis (ditolyl phosphate). These substituents may be the same or different, and may be further substituted. Also, it may be a mix of alkyl, cycloalkyl, and aryl groups, and the substituents may be covalently bonded.
[0044] 更にリン酸エステルの部分構造力 ポリマーの一部、或いは規則的にペンダントさ れていても良ぐまた酸化防止剤、酸捕捉剤、紫外線吸収剤等の添加剤の分子構造 の一部に導入されていても良い。上記化合物の中では、リン酸ァリールエステル、ァ リーレンビス（ジァリールホスフェート）が好ましぐ具体的にはトリフエ-ルホスフェート 、フエ二レンビス（ジフエ-ルホスフェート）が好まし 、。 [0044] Further, partial structural strength of phosphate ester Part of polymer or part of molecular structure of additives such as antioxidants, acid scavengers, UV absorbers etc. May be introduced. Among the above compounds, phosphoryl ester and arylene bis (diaryl phosphate) are preferred. Specifically, triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferred.
[0045] エチレングリコールエステル系の可塑剤：具体的には、エチレングリコールジァセテ ート、エチレングリコールジブチレート等のエチレングリコーノレアノレキノレエステノレ系の 可塑剤、エチレングリコールジシクロプロピルカルボキシレート、エチレングリコールジ シクロへキルカルボキシレート等のエチレングリコールシクロアルキルエステル系の可 塑剤、エチレングリコールジベンゾエート、エチレングリコールジ 4ーメチノレべンゾェ ート等のエチレングリコールァリールエステル系の可塑剤が挙げられる。これらアルキ レート基、シクロアルキレート基、ァリレート基は、同一でもあっても異なっていてもよく 、更に置換されていても良い。またアルキレート基、シクロアルキレート基、ァリレート 基のミックスでも良ぐまたこれら置換基同志が共有結合で結合していても良い。更に エチレングリコール部も置換されていても良ぐエチレングリコールエステルの部分構 造力 ポリマーの一部、或いは規則的にペンダントされていても良ぐまた酸化防止 剤、酸捕捉剤、紫外線吸収剤等の添加剤の分子構造の一部に導入されていても良 い。  [0045] Ethylene glycol ester-based plasticizer: Specifically, ethylene glycol dioleopropylene ester plasticizer such as ethylene glycol diacetate and ethylene glycol dibutyrate, ethylene glycol dicyclopropyl carboxylate And ethylene glycol cycloalkyl ester plasticizers such as ethylene glycol dicyclohexylcarboxylate, and ethylene glycol diaryl ester plasticizers such as ethylene glycol dibenzoate and ethylene glycol di-4-methylenobenzoate. . These alkylate group, cycloalkylate group and arylate group may be the same or different, and may be further substituted. Further, a mixture of alkylate group, cycloalkylate group and arylate group may be used, and these substituents may be bonded by a covalent bond. In addition, the ethylene glycol ester may have a substituted partial structure strength of an ethylene glycol ester. It may be part of a polymer or may be regularly pendant. Also, an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into a part of the molecular structure of the additive.
[0046] グリセリンエステル系の可塑剤：具体的にはトリァセチン、トリブチリン、グリセリンジ アセテートカプリレート、グリセリンォレートプロピオネート等のグリセリンアルキルエス テル、グリセリントリシクロプロピルカルボキシレート、グリセリントリシクロへキシルカル ボキシレート等のグリセリンシクロアルキルエステル、グリセリントリべンゾエート、グリセ リン 4 メチルベンゾエート等のグリセリンァリールエステル、ジグリセリンテトラァセチ レート、ジグリセリンテトラプロピオネート、ジグリセリンアセテートトリカプリレート、ジグ リセリンテトララウレート、等のジグリセリンアルキルエステル、ジグリセリンテトラシクロ ブチルカルボキシレート、ジグリセリンテトラシクロペンチルカルボキシレート等のジグ リセリンシクロアルキルエステル、ジグリセリンテトラべンゾエート、ジグリセリン 3—メチ ルベンゾエート等のジグリセリンァリールエステル等が挙げられる。これらアルキレート 基、シクロアルキルカルボキシレート基、ァリレート基は、同一でもあっても異なってい てもよく、更に置換されていても良い。またアルキレート基、シクロアルキルカルボキシ レート基、ァリレート基のミックスでも良ぐまたこれら置換基同志が共有結合で結合し ていても良い。更にグリセリン、ジグリセリン部も置換されていても良ぐグリセリンエス テル、ジグリセリンエステルの部分構造力 ポリマーの一部、或いは規則的にベンダ ントされていても良ぐまた酸化防止剤、酸捕捉剤、紫外線吸収剤等の添加剤の分 子構造の一部に導入されて 、ても良 、。 [0046] Glycerin ester plasticizers: specifically glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, glycerol tricyclopropyl carboxylate, glycerol tricyclohexyl carboxylate Glycerin cycloalkyl ester, glycerin tribenzoate, glycerin 4-methylbenzoate, etc. glycerin aryl ester, diglycerin tetraacetyl Diglycerin cycloalkyl esters such as diglycerin alkyl esters such as diglycerin tetrapropionate, diglycerin acetate tricaprylate, diglycerin tetralaurate, diglycerin tetracyclobutyl carboxylate, diglycerin tetracyclopentyl carboxylate And diglycerin tetrabenzoate such as diglycerin tetrabenzoate and diglycerin 3-methylbenzoate. These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. Further, a mixture of alkylate group, cycloalkyl carboxylate group and arylate group may be used, and these substituents may be bonded by a covalent bond. Furthermore, glycerin ester and diglycerin part may be substituted glycerin ester, diglycerin ester partial structural strength part of polymer, or may be regularly bent, also antioxidant, acid scavenger It may be introduced into a part of the molecular structure of additives such as UV absorbers.
[0047] 多価アルコールエステル系の可塑剤：具体的には、特開 2003— 12823号公報の 段落 30〜33記載の多価アルコールエステル系可塑剤が挙げられる。  [0047] Polyhydric alcohol ester plasticizer: Specific examples include polyhydric alcohol ester plasticizers described in paragraphs 30 to 33 of JP-A No. 2003-12823.
[0048] これらアルキレート基、シクロアルキルカルボキシレート基、ァリレート基は、同一で もあっても異なっていてもよく、更に置換されていても良い。またアルキレート基、シク 口アルキルカルボキシレート基、ァリレート基のミックスでも良ぐまたこれら置換基同 志が共有結合で結合して ヽても良 ヽ。更に多価アルコール部も置換されて!、ても良 ぐ多価アルコールの部分構造力 ポリマーの一部、或いは規則的にペンダントされ ていても良ぐまた酸化防止剤、酸捕捉剤、紫外線吸収剤等の添加剤の分子構造の 一部に導入されて 、ても良 、。  [0048] These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. In addition, a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group may be used, and these substituents may be covalently bonded. In addition, the polyhydric alcohol part may be substituted! Partial polyhydric alcohol structure may be part of the polymer or may be regularly pendant Antioxidants, acid scavengers, UV absorbers It may be introduced into a part of the molecular structure of the additive.
[0049] ジカルボン酸エステル系の可塑剤：具体的には、ジドデシルマロネート（C1)、ジォ クチルアジペート (C4)、ジブチルセバケート (C8)等のアルキルジカルボン酸アルキ ルエステル系の可塑剤、ジシクロペンチルサクシネート、ジシクロへキシルアジーぺ ート等のアルキルジカルボン酸シクロアルキルエステル系の可塑剤、ジフエ-ルサク シネート、ジ 4 メチルフエ-ルグルタレート等のアルキルジカルボン酸ァリールエス テル系の可塑剤、ジへキシルー 1, 4ーシクロへキサンジカルボキシレート、ジデシル ビシクロ [2. 2. 1]ヘプタン 2, 3 ジカルボキシレート等のシクロアルキルジカルボ ン酸アルキルエステル系の可塑剤、ジシクロへキシルー 1, 2—シクロブタンジカルボ キシレート、ジシクロプロピノレー 1, 2—シクロへキシノレジ力ノレボキシレート等のシクロ アルキルジカルボン酸シクロアルキルエステル系の可塑剤、ジフエ-ルー 1, 1ーシク 口プロピルジカルボキシレート、ジ 2 ナフチルー 1, 4ーシクロへキサンジカルボキシ レート等のシクロアルキルジカルボン酸ァリールエステル系の可塑剤、ジェチルフタ レート、ジメチルフタレート、ジォクチルフタレート、ジブチルフタレート、ジー 2—ェチ ルへキシルフタレート等のァリールジカルボン酸アルキルエステル系の可塑剤、ジシ クロプロピルフタレート、ジシクロへキシルフタレート等のァリールジカルボン酸シクロ アルキルエステル系の可塑剤、ジフエ-ルフタレート、ジ 4 メチルフエ-ルフタレート 等のァリールジカルボン酸ァリールエステル系の可塑剤が挙げられる。これらアルコ キシ基、シクロアルコキシ基は、同一でもあっても異なっていてもよぐまた一置換でも 良ぐこれらの置換基は更に置換されていても良い。アルキル基、シクロアルキル基 はミックスでも良ぐまたこれら置換基同志が共有結合で結合していても良い。更にフ タル酸の芳香環も置換されていて良ぐダイマー、トリマー、テトラマー等の多量体で も良い。またフタル酸エステルの部分構造力 ポリマーの一部、或いは規則的にポリ マーへペンダントされていても良ぐ酸化防止剤、酸捕捉剤、紫外線吸収剤等の添 加剤の分子構造の一部に導入されて ヽても良 、。 [0049] Dicarboxylic acid ester plasticizer: Specifically, alkyl dicarboxylic acid alkyl ester plasticizer such as didodecyl malonate (C1), dioctyl adipate (C4), dibutyl sebacate (C8), Alkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclopentyl succinate and dicyclohexyl adipate, alkyl dicarboxylic acid aryl ester plasticizers such as diphenyl succinate and di-4-methylphenol glutarate, dihexyl , 4-cyclohexanedicarboxylate, didecyl bicyclo [2.2.1] heptane 2,3 dicarboxylate Alkyl ester plasticizers such as dicyclohexyl 1,2-cyclobutane dicarboxylate and dicyclopropinole 1,2-cyclohexinoresiency nore oxylate, and the like. -Lu 1,1-sic propyl dicarboxylate, di-2-naphthyl 1,4-cyclohexanedicarboxylate and other cycloalkyldicarboxylic acid aryl ester plasticizers, jetyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl Alyl dicarboxylic acid alkyl ester plasticizers such as phthalate and di-2-ethyl hexyl phthalate, diaryl carboxylic acid cycloalkyl ester plasticizers such as dicyclopropyl phthalate and dicyclohexyl phthalate, diphenol Rate, di 4 Mechirufue - § reel dicarboxylic acid § reel ester based plasticizers such as Rufutareto like. These alkoxy groups and cycloalkoxy groups may be the same or different, and may be mono-substituted. These substituents may be further substituted. The alkyl group and cycloalkyl group may be mixed, or these substituents may be covalently bonded. In addition, the aromatic ring of phthalic acid may be substituted and may be a multimer such as a dimer, trimer or tetramer. It is also part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc., which may be partly polymerized or partially pendant into the polymer. It is okay to be introduced.
多価カルボン酸エステル系の可塑剤：具体的には、トリドデシルトリ力ルバレート、ト リブチルー meso ブタン—1, 2, 3, 4ーテトラカルボキシレート等のアルキル多価力 ルボン酸アルキルエステル系の可塑剤、トリシクロへキシルトリ力ルバレート、トリシクロ プロピル— 2 ヒドロキシ— 1, 2, 3 プロパントリカルボキシレート等のアルキル多価 カルボン酸シクロアルキルエステル系の可塑剤、トリフエ-ル 2 ヒドロキシ 1, 2, 3 —プロパントリカルボキシレート、テトラ 3—メチルフエ-ルテトラヒドロフラン一 2, 3, 4 , 5—テトラカルボキシレート等のアルキル多価カルボン酸ァリールエステル系の可塑 剤、テトラへキシルー 1, 2, 3, 4ーシクロブタンテトラカルボキシレート、テトラブチル —1, 2, 3, 4ーシクロペンタンテトラカルボキシレート等のシクロアルキル多価カルボ ン酸アルキルエステル系の可塑剤、テトラシクロプロピル 1, 2, 3, 4ーシクロブタン テトラ力ノレボキシレート、トリシクロへキシノレ 1, 3, 5 シクロへキシノレトリ力ノレボキシ レート等のシクロアルキル多価カルボン酸シクロアルキルエステル系の可塑剤、トリフ ェ-ルー 1, 3, 5 シクロへキシルトリカルボキシレート、へキサ 4 メチルフエ-ルー 1, 2, 3, 4, 5, 6 シクロへキシルへキサカルボキシレート等のシクロアルキル多価 カルボン酸ァリールエステル系の可塑剤、トリドデシルベンゼン 1, 2, 4 トリカル ボキシレート、テトラオクチルベンゼン 1, 2, 4, 5—テトラカルボキシレート等のァリ ール多価カルボン酸アルキルエステル系の可塑剤、トリシクロペンチルベンゼン 1 , 3, 5 トリカルボキシレート、テトラシクロへキシルベンゼン一 1, 2, 3, 5—テトラ力 ルボキシレート等のァリール多価カルボン酸シクロアルキルエステル系の可塑剤トリ フエ-ルベンゼン 1, 3, 5—テトラカルトキシレート、へキサ 4 メチルフエ-ルペン ゼンー 1, 2, 3, 4, 5, 6 へキサカルボキシレート等のァリール多価カルボン酸ァリ ールエステル系の可塑剤が挙げられる。これらアルコキシ基、シクロアルコキシ基は、 同一でもあっても異なっていてもよぐまた一置換でも良ぐこれらの置換基は更に置 換されていても良い。アルキル基、シクロアルキル基はミックスでも良ぐまたこれら置 換基同志が共有結合で結合して!/ヽても良!ヽ。更にフタル酸の芳香環も置換されて 、 て良ぐダイマー、トリマー、テトラマー等の多量体でも良い。またフタル酸エステルの 部分構造が、ポリマーの一部、或いは規則的にポリマーへペンダントされていても良 ぐ酸化防止剤、酸捕捉剤、紫外線吸収剤等の添加剤の分子構造の一部に導入さ れていても良い。 Polycarboxylic acid ester plasticizers: Specifically, alkyl polyhydric strengths such as tridodecyl triforce ruvalate, tributyl meso butane-1, 2, 3, 4-tetracarboxylate, etc. Alkyl polyvalent carboxylic acid cycloalkyl ester based plasticizers such as tricyclohexyl triforce ruvalate, tricyclopropyl-2-hydroxy-1, 2, 3 propane tricarboxylate, triphenyl 2-hydroxy 1, 2, 3 —propane Alkyl polycarboxylic acid aryl ester plasticizers such as tricarboxylate, tetra-3-methylphenoltetrahydrofuran 1, 2, 3, 4, 5-tetracarboxylate, tetrahexyl 1,2,3,4-cyclobutane Tetracarboxylate, tetrabutyl — 1, 2, 3, 4-cyclopentanetetracarboxylate, etc. Black alkyl polyhydric carboxyalkyl phosphate alkyl ester plasticizers, tetra cyclopropyl 1, 2, 3, 4 Shikurobutan tetra force Norebokishireto, Kishinore 1, 3, 5 Kishinoretori force Norebokishi to cycloheteroalkyl tricyclo Cycloalkyl polycarboxylic acid cycloalkyl ester plasticizers such as rate, triphenyl 1, 3, 5 cyclohexyl tricarboxylate, hexamethyl 4-methylphenol 1, 2, 3, 4, 5, 6 Cycloalkyl polycarboxylic acid aryl ester plasticizers such as cyclohexylhexacarboxylate, tridodecylbenzene 1, 2, 4 tricarboxylate, tetraoctylbenzene 1, 2, 4, 5-tetracarboxylate, etc. Alkyl polycarboxylic acid alkyl ester plasticizers, tricyclopentylbenzene 1, 3, 5 tricarboxylate, tetracyclohexylbenzene 1, 2, 3, 5-tetra force polycarboxylic acid such as ruboxylate Cycloalkyl ester plasticizers Triphenylbenzene 1, 3, 5-Tetracartoxylate, Hexa 4 Methylphenol Hmm 1, 2, 3, 4, 5, Ariru polycarboxylic acid § Li Ruesuteru based plasticizers hexa carboxylate to 6. These alkoxy groups and cycloalkoxy groups may be the same or different and may be mono-substituted, and these substituents may be further substituted. Alkyl groups and cycloalkyl groups may be mixed, and these substituents may be bonded together via a covalent bond! Further, the aromatic ring of phthalic acid may be substituted, and a polymer such as a good dimer, trimer or tetramer may be used. In addition, the partial structure of the phthalate ester is introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc., which may be partly pendant into the polymer. It may be done.
ポリマー可塑剤:具体的には、脂肪族炭化水素系ポリマー、脂環式炭化水素系ポリ マー、ポリアクリル酸ェチル、ポリメタクリル酸メチル等のアクリル系ポリマー、ポリビ- ルイソブチルエーテル、ポリ N—ビュルピロリドン等のビュル系ポリマー、ポリスチレン 、ポリ 4ーヒドロキシスチレン等のスチレン系ポリマー、ポリブチレンサクシネート、ポリ エチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリエチレンォキ シド、ポリプロピレンォキシド等のポリエーテル、ポリアミド、ポリウレタン、ポリウレァ等 が挙げられる。数平均分子量は、 1000〜500000程度が好ましぐ特に好ましくは、 5000〜200000である。 1000以下では揮発'性に問題力 S生じ、 500000を超えると 可塑ィ匕能力が低下し、セルロースエステル誘導体組成物の機械的性質に悪影響を 及ぼす。これらポリマー可塑剤は 1種の繰り返し単位力 なる単独重合体でも、複数 の繰り返し構造体を有する共重合体でも良い。また、上記ポリマーを 2種以上併用し て用いても良ぐ他の可塑剤、酸化防止剤、酸捕捉剤、紫外線吸収剤、滑り剤及び マット剤等を含有させても良い。 Polymer plasticizers: Specific examples include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, acrylic polymers such as polyethyl acrylate and polymethyl methacrylate, polyvinyl isobutyl ether, and poly N-butyl. Buryl polymers such as pyrrolidone, styrene polymers such as polystyrene and poly-4-hydroxystyrene, polybutylene succinate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide, polyamides , Polyurethane, polyurea and the like. The number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5000 to 200,000. Below 1000, a problem arises in volatility, and when it exceeds 500,000, the plasticizing ability decreases, and the mechanical properties of the cellulose ester derivative composition are adversely affected. These polymer plasticizers may be homopolymers with one type of repeating unit force. A copolymer having a repeating structure of Further, other plasticizers, antioxidants, acid scavengers, ultraviolet absorbers, slipping agents, matting agents, and the like which may be used in combination of two or more of the above polymers may be contained.
[0052] 上記可塑剤の中でも熱溶融時に揮発成分を生成しないことが一般的には好ましい 。具体的には特表平 6— 501040号に記載されている不揮発性リン酸エステルが挙 げられ、例えばァリーレンビス（ジァリールホスフェート）エステルや上記例示化合物 の中ではトリメチロールプロパントリべンゾエート等が好ましいがこれらに限定されるも のではない。揮発成分が上記可塑剤の熱分解によるとき、上記可塑剤の熱分解温度 Td (l. 0)は、 1. 0質量％減少したときの温度と定義すると、フィルム形成材料の溶 融温度よりも高いことが求められる。可塑剤は、上記目的のために、セルロースエステ ルに対する添加量が他のフィルム構成材料よりも多ぐ揮発成分の存在は得られるフ イルムの品質に与える劣位となる影響が大きいためである。熱分解温度 Td (l. 0)は 、市販の示差熱重量分析 (TG— DTA)装置で測定することが出来る。  [0052] Among the plasticizers, it is generally preferable that no volatile component is generated during heat melting. Specific examples include non-volatile phosphate esters described in JP-A-6-501040, and examples include arylene bis (diaryl phosphate) esters and trimethylolpropane tribenzoate among the above exemplified compounds. Although it is preferable, it is not limited to these. When the volatile component is due to the thermal decomposition of the plasticizer, the thermal decomposition temperature Td (l. 0) of the plasticizer is defined as the temperature at which the mass decreases by 1.0% by mass, than the melting temperature of the film-forming material. High is required. This is because, for the purpose described above, the presence of a volatile component in which the amount of the plasticizer added to the cellulose ester is larger than that of other film constituent materials has a great influence on the quality of the obtained film. The thermal decomposition temperature Td (l. 0) can be measured with a commercially available differential thermogravimetric analysis (TG—DTA) apparatus.
[0053] (セルロースエステル榭脂）  [0053] (cellulose ester resin)
本発明に係るセルロースエステル榭脂は、セルロースエステルの構造を示し、脂肪 酸ァシル基、置換もしくは無置換の芳香族ァシル基の中から少なくともいずれかの構 造を含む、セルロースの前記単独または混合酸エステルであることが好ま 、。  The cellulose ester resin according to the present invention shows the structure of cellulose ester and contains at least one structure selected from the group consisting of a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group. Preferred to be an ester.
[0054] 以下、本発明の目的を満たす上で有用なセルロースエステルにつ 、て例示するが これらに限定されるものではない。  [0054] Hereinafter, cellulose esters useful for satisfying the object of the present invention will be exemplified, but the present invention is not limited thereto.
[0055] 芳香族ァシル基にぉ 、て、芳香族環がベンゼン環であるとき、ベンゼン環の置換基 の例としてハロゲン原子、シァ入アルキル基、アルコキシ基、ァリール基、ァリールォ キシ基、ァシル基、カルボンアミド基、スルホンアミド基、ウレイド基、ァラルキル基、二 トロ、アルコキシカルボ-ル基、ァリールォキシカルボ-ル基、ァラルキルォキシカル ボ-ル基、力ルバモイル基、スルファモイル基、ァシルォキシ基、ァルケ-ル基、アル キ-ル基、アルキルスルホ-ル基、ァリールスルホ-ル基、アルキルォキシスルホ- ル基、ァリールォキシスルホ -ル基、アルキルスルホ -ルォキシ基及びァリールォキ シスルホ -ル基、 S— R、 一 NH— CO— OR、 一 PH— R、 一 P (— R) 、 一 PH— O  [0055] When the aromatic ring is a benzene ring and the aromatic ring is a benzene ring, examples of the substituent of the benzene ring include a halogen atom, a cyanoalkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group. , Carbonamido group, sulfonamido group, ureido group, aralkyl group, nitrogen, alkoxy carboxylic group, aralkyl carboxylic group, aralkyl oxy carboxylic group, strong rubamoyl group, sulfamoyl group , An acyloxy group, an alkyl group, an alkyl group, an alkyl sulfonyl group, an aryl sulfonyl group, an alkyloxy sulfonyl group, an allyloxy sulfonyl group, an alkyl sulfonyl group and an aralkyl group. Cysulfol group, S—R, 1 NH—CO—OR, 1 PH—R, 1 P (—R), 1 PH—O
2  2
一 R、 一 P (一 R) (— O— R)ゝ -P (-O-R) 、 一 PH ( = 0)— R— P ( = 0) (— R) 、 一 PH ( = One R, One P (One R) (— O— R) ゝ -P (-OR), One PH (= 0) — R— P (= 0) (— R), One PH (=
2 2  twenty two
O)— O— R、 一 P ( = 0) (— R) (— O— R)ゝ 一 P ( = 0) (-O-R) 、 一 O— PH ( = 0  O) — O— R, one P (= 0) (— R) (— O— R) ゝ one P (= 0) (-O-R), one O— PH (= 0
2  2
) 一 R、 一 O— P ( = 0) (— R) — O— PH ( = 0) -O-R, 一 O— P ( = 0) (— R) (—  ) One R, One O— P (= 0) (— R) — O— PH (= 0) -O-R, One O— P (= 0) (— R) (—
2  2
O-R) , O— P ( = 0) (-O-R) 、 -NH  O-R), O— P (= 0) (-O-R), -NH
2  2
一 PH ( = 0)— R、 一 NH— P ( = 0) (— R) (— O— R)、 一 NH— P ( = 0) (— O— R) 、 一 SiH— R、 -SiH (-R) 、 一 Si (— R) 、 一 O— SiH—  One PH (= 0) — R, One NH— P (= 0) (— R) (— O— R), One NH— P (= 0) (— O— R), One SiH— R, —SiH (-R), 1 Si (— R), 1 O— SiH—
2 2 2 3 2  2 2 2 3 2
R、 -O-SiH (-R)及び— O— Si (— R) が含まれる。上記 Rは脂肪族基、芳香族  R, —O—SiH (—R) and —O—Si (—R) are included. R is aliphatic group, aromatic
2 3  twenty three
基またはへテロ環基である。置換基の数は、一個〜五個であることが好ましぐ一個 〜四個であることがより好ましぐ一個〜三個であることが更に好ましぐ一個または二 個であることが最も好ましい。置換基としては、ハロゲン原子、シァ入アルキル基、ァ ルコキシ基、ァリール基、ァリールォキシ基、ァシル基、カルボンアミド基、スルホンァ ミド基及びウレイド基が好ましぐハロゲン原子、シァ入アルキル基、アルコキシ基、 ァリールォキシ基、ァシル基及びカルボンアミド基がより好ましぐハロゲン原子、シァ 入アルキル基、アルコキシ基及びァリールォキシ基が更に好ましぐハロゲン原子、 アルキル基及びアルコキシ基が最も好まし 、。  A group or a heterocyclic group. The number of substituents is preferably one to five, one to four, more preferably one to three, and even more preferably one or two. preferable. Substituents include halogen atoms, cyanide alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, carbonamido groups, sulfonamido groups and ureido groups, halogen atoms, cyanide alkyl groups, alkoxy groups. A halogen atom, an alkyl group, an alkoxy group, and an aryl group, more preferably a halogen atom, an alkyl group, and an alkoxy group, more preferably a halogen atom, a silylated alkyl group, an alkoxy group, and an aryloxy group.
[0056] 上記ハロゲン原子には、フッ素原子、塩素原子、臭素原子及びヨウ素原子が含ま れる。上記アルキル基は、環状構造或いは分岐を有していてもよい。アルキル基の 炭素原子数は、 1〜20であることが好ましぐ 1〜12であることがより好ましぐ 1〜6で あることが更に好ましぐ 1〜4であることが最も好ましい。アルキル基の例には、メチ ル、ェチル、プロピル、イソプロピル、ブチル、 t—ブチル、へキシル、シクロへキシル 、ォクチル及び 2—ェチルへキシルが含まれる。上記アルコキシ基は、環状構造或い は分岐を有していてもよい。アルコキシ基の炭素原子数は、 1〜20であることが好ま しぐ 1〜12であることがより好ましぐ 1〜6であることが更に好ましぐ 1〜4であること が最も好ましい。アルコキシ基は、更に別のアルコキシ基で置換されていてもよい。ァ ノレコキシ基の^ Jには、メトキシ、エトキシ、 2—メトキシエトキシ、 2—メトキシー 2—エト キシエトキシ、ブチルォキシ、へキシルォキシ及びォクチルォキシが含まれる。  [0056] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group may have a cyclic structure or a branch. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-12, even more preferably 1-6, and most preferably 1-4. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl. The alkoxy group may have a cyclic structure or a branch. The number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-12, even more preferably 1-6, and most preferably 1-4. The alkoxy group may be further substituted with another alkoxy group. ^ J of the vinyloxy group includes methoxy, ethoxy, 2-methoxyethoxy, 2-methoxy-2-ethoxyethoxy, butoxy, hexyloxy and octyloxy.
[0057] 上記ァリール基の炭素原子数は、 6〜20であることが好ましぐ 6〜12であることが 更に好ましい。ァリール基の例には、フエニル及びナフチルが含まれる。上記ァリー ルォキシ基の炭素原子数は、 6〜20であることが好ましぐ 6〜12であることが更に好 ましい。ァリールォキシ基の例には、フエノキシ及びナフトキシが含まれる。上記ァシ ル基の炭素原子数は、 1〜20であることが好ましぐ 1〜12であることが更に好ましい 。ァシル基の例には、ホルミル、ァセチル及びベンゾィルが含まれる。上記カルボン アミド基の炭素原子数は、 1〜20であることが好ましぐ 1〜12であることが更に好ま しい。カルボンアミド基の例には、ァセトアミド及びべンズアミドが含まれる。上記スル ホンアミド基の炭素原子数は、 1〜20であることが好ましぐ 1〜12であることが更に 好ましい。スルホンアミド基の例には、メタンスルホンアミド、ベンゼンスルホンアミド及 び p—トルエンスルホンアミドが含まれる。上記ウレイド基の炭素原子数は、 1〜20で あることが好ましぐ 1〜 12であることが更に好ましい。ウレイド基の例には、（無置換） ウレイドが含まれる。 [0057] The number of carbon atoms in the aryl group is preferably 6-20, and more preferably 6-12. Examples of aryl groups include phenyl and naphthyl. Above The number of carbon atoms in the ruoxy group is preferably 6-20, and more preferably 6-12. Examples of the aryloxy group include phenoxy and naphthoxy. The number of carbon atoms in the acyl group is preferably 1-20, and more preferably 1-12. Examples of the acyl group include formyl, acetyl and benzoyl. The number of carbon atoms of the carboxamide group is preferably 1-20, and more preferably 1-12. Examples of the carbonamido group include acetamide and benzamide. The number of carbon atoms of the sulfonamide group is preferably 1-20, and more preferably 1-12. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and p-toluenesulfonamide. The number of carbon atoms of the ureido group is preferably 1-20, and more preferably 1-12. Examples of ureido groups include (unsubstituted) ureido.
[0058] 上記ァラルキル基の炭素原子数は、 7〜20であることが好ましぐ 7〜 12であること が更に好ましい。ァラルキル基の例には、ベンジル、フエネチル及びナフチルメチル が含まれる。上記アルコキシカルボニル基の炭素原子数は、 1〜20であることが好ま しぐ 2〜12であることが更に好ましい。アルコキシカルボ-ル基の例には、メトキシカ ルポ-ルが含まれる。上記ァリールォキシカルボ-ル基の炭素原子数は、 7〜20で あることが好ましぐ 7〜 12であることが更に好ましい。ァリールォキシカルボ-ル基の 例には、フエノキシカルボ-ルが含まれる。上記ァラルキルォキシカルボ-ル基の炭 素原子数は、 8〜20であることが好ましぐ 8〜12であることが更に好ましい。ァラル キルォキシカルボ-ル基の例には、ベンジルォキシカルボ-ルが含まれる。上記力 ルバモイル基の炭素原子数は、 1〜20であることが好ましぐ 1〜12であることが更に 好まし 、。力ルバモイル基の例には、（無置換)力ルバモイル及び N—メチルカルバ モイルが含まれる。上記スルファモイル基の炭素原子数は、 20以下であることが好ま しぐ 12以下であることが更に好ましい。スルファモイル基の例には、（無置換)スルフ ァモイル及び N—メチルスルファモイルが含まれる。上記ァシルォキシ基の炭素原子 数は、 1〜20であることが好ましぐ 2〜12であることが更に好ましい。ァシルォキシ 基の例には、ァセトキシ及びベンゾィルォキシが含まれる。  [0058] The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. Examples of aralkyl groups include benzyl, phenethyl and naphthylmethyl. The alkoxycarbonyl group has preferably 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbon. The number of carbon atoms of the aryloxycarbonyl group is preferably 7-20, and more preferably 7-12. Examples of aryloxy groups include phenoxycarbons. The number of carbon atoms of the aralkyloxycarbonyl group is preferably 8 to 20, and more preferably 8 to 12. Examples of the aralkyloxycarbonyl group include benzyloxycarbonyl. The above-mentioned force The number of carbon atoms of the rubermoyl group is preferably 1-20, more preferably 1-12. Examples of force rubamoyl groups include (unsubstituted) force rubamoyl and N-methylcarbamoyl. The number of carbon atoms in the sulfamoyl group is preferably 20 or less, and more preferably 12 or less. Examples of the sulfamoyl group include (unsubstituted) sulfamoyl and N-methylsulfamoyl. The number of carbon atoms in the acyloxy group is preferably 1-20, and more preferably 2-12. Examples of the acyloxy group include acetoxy and benzoyloxy.
[0059] 上記ァルケ-ル基の炭素原子数は、 2〜20であることが好ましぐ 2〜 12であること が更に好ましい。ァルケ-ル基の例には、ビニル、ァリル及びイソプロべ-ルが含ま れる。上記アルキ-ル基の炭素原子数は、 2〜20であることが好ましぐ 2〜12である ことが更に好ましい。アルキ-ル基の例には、チェ-ルが含まれる。上記アルキルス ルホニル基の炭素原子数は、 1〜20であることが好ましぐ 1〜12であることが更に好 ましい。上記ァリールスルホ-ル基の炭素原子数は、 6〜20であることが好ましぐ 6 〜12であることが更に好まし!/、。上記アルキルォキシスルホ -ル基の炭素原子数は 、 1〜20であることが好ましぐ 1〜12であることが更に好ましい。上記ァリールォキシ スルホ-ル基の炭素原子数は、 6〜20であることが好ましぐ 6〜12であることが更に 好ましい。上記アルキルスルホ-ルォキシ基の炭素原子数は、 1〜20であることが好 ましぐ 1〜 12であることが更に好ましい。上記ァリールォキシスルホ -ル基の炭素原 子数は、 6〜20であることが好ましぐ 6〜12であることが更に好ましい。 [0059] The number of carbon atoms in the alkenyl group is preferably 2 to 20, and preferably 2 to 12. Is more preferable. Examples of alkenyl groups include vinyl, aryl and isopropyl. The number of carbon atoms of the alkyl group is preferably 2-20, and more preferably 2-12. Examples of alkyl groups include chaels. The number of carbon atoms of the alkylsulfonyl group is preferably 1-20, and more preferably 1-12. The number of carbon atoms in the arylaryl group is preferably 6-20, more preferably 6-12! /. The number of carbon atoms of the alkyloxysulfol group is preferably 1-20, and more preferably 1-12. The aryloxy sulfol group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The number of carbon atoms of the alkylsulfooxy group is preferably 1-20, and more preferably 1-12. The number of carbon atoms of the aryloxysulfol group is preferably 6-20, and more preferably 6-12.
[0060] 本発明のセルロースエステルにおいて、セルロースの水酸基部分の水素原子が脂 肪族ァシル基との脂肪酸エステルであるとき、脂肪族ァシル基は炭素原子数が 2〜2 0で具体的にはァセチル、プロピオニル、ブチリル、イソブチリル、バレリル、ビバロイ ル、へキサノィル、オタタノィル、ラウロイル、ステアロイル等が挙げられる。  [0060] In the cellulose ester of the present invention, when the hydrogen atom of the hydroxyl group of cellulose is a fatty acid ester with an aliphatic acyl group, the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetylyl. Propionyl, butyryl, isobutyryl, valeryl, bivalol, hexanoyl, otatanyl, lauroyl, stearoyl and the like.
[0061] 本発明において前記脂肪族ァシル基とは更に置換基を有するものも包含する意味 であり、置換基としては上述の芳香族ァシル基において、芳香族環がベンゼン環で あるとき、ベンゼン環の置換基として例示したものが挙げられる。  [0061] In the present invention, the term "aliphatic acyl group" is intended to include those further having a substituent. Examples of the substituent include a benzene ring when the aromatic ring is a benzene ring in the above-mentioned aromatic acyl group. What was illustrated as a substituent of is mentioned.
[0062] また、上記セルロースエステルのエステルイ匕された置換基が芳香環であるとき、芳 香族環に置換する置換基 Xの数は 0または 1〜5個であり、好ましくは 1〜3個で、特 に好ましいのは 1又は 2個である。更に、芳香族環に置換する置換基の数が 2個以上 の時、互いに同じでも異なっていてもよいが、また、互いに連結して縮合多環化合物 (例えばナフタレン、インデン、インダン、フエナントレン、キノリン、イソキノリン、クロメ ン、クロマン、フタラジン、アタリジン、インドール、インドリンなど）を形成してもよい。  [0062] When the esterified substituent of the cellulose ester is an aromatic ring, the number of substituents X substituted on the aromatic ring is 0 or 1 to 5, preferably 1 to 3. Particularly preferred is 1 or 2. Further, when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline). , Isoquinoline, chromene, chroman, phthalazine, atalidine, indole, indoline, etc.).
[0063] 上記セルロースエステルにおいて置換もしくは無置換の脂肪族ァシル基、置換もし くは無置換の芳香族ァシル基の少なくともいずれか 1種選択された構造を有する構 造を有することが本発明のセルロースエステルに用いる構造として用いられ、これら は、セルロースの単独または混合酸エステルでもよぐ 2種以上のセルロースエステル を混合して用いてもよい。 [0063] The cellulose of the present invention has a structure having a structure selected from at least one of a substituted or unsubstituted aliphatic acyl group and a substituted or unsubstituted aromatic acyl group in the cellulose ester. Used as a structure for esters, these may be cellulose single or mixed acid esters. May be used in combination.
[0064] 本発明の光学フィルムを構成する前記セルロースエステルにおいて、セルロースァ セテート、セノレロースプロピオネート、セノレロースブチレート、セノレロースアセテートプ 口ピオネート、セルロースアセテートブチレート、セルロースアセテートフタレート、及 びセルロースフタレートから選ばれる少なくとも 1種であることが好まし 、。  [0064] In the cellulose ester constituting the optical film of the present invention, cellulose acetate, cenololose propionate, cenololose butyrate, cenololose acetate pionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose It is preferred that it is at least one selected from phthalates.
[0065] これらの中で特に好まし!/、セルロースエステルは、セルロースアセテート、セルロー スプロピオネート、セノレロースブチレート、セノレロースアセテートプロピオネートゃセノレ ロースアセテートブチレートが挙げられる。  [0065] Among them, cellulose ester, cellulose ester, cellulose propionate, senorelose butyrate, senorelose acetate propionate and senocellulose acetate butyrate are particularly preferred!
[0066] 混合脂肪酸エステルの置換度として、更に好ましいセルロースアセテートプロピオ ネートやセルロースアセテートブチレートの低級脂肪酸エステルは、炭素原子数 2〜 4のァシル基を置換基として有し、ァセチル基の置換度を Xとし、プロピオニル基又は プチリル基の置換度を Yとした時、下記式 (I)及び (Π)を同時に満たすセルロースェ ステルを含むセルロース榭脂であることが好ましい。  [0066] As the degree of substitution of the mixed fatty acid ester, more preferable cellulose acetate propionate and lower fatty acid ester of cellulose acetate butyrate have an acyl group having 2 to 4 carbon atoms as a substituent, and the degree of substitution of the acetyl group. Is a cellulose resin containing cellulose ester that simultaneously satisfies the following formulas (I) and (Π), where X is X and the substitution degree of propionyl group or propylyl group is Y.
[0067] 式（I) 2. 6≤X+Y≤3. 0  [0067] Formula (I) 2. 6≤X + Y≤3.0
式（Π) 1. 0≤Χ≤2. 5  Formula (Π) 1. 0≤Χ≤2.5
この内特にセルロースアセテートプロピオネートが好ましく用いられ、中でも 1. 9≤ Χ≤2. 5であり、 0. 1≤Υ≤0. 9であることが好ましい。上記ァシル基で置換されてい な 、部分は通常水酸基として存在して 、るのものである。これらは公知の方法で合成 することが出来る。  Of these, cellulose acetate propionate is particularly preferably used. Among them, 1.9≤ 、 ≤2.5, and preferably 0.1≤Υ≤0.9. If not substituted with the above acyl group, the moiety is usually present as a hydroxyl group. These can be synthesized by known methods.
[0068] 更に、本発明で用いられるセルロースエステルは、重量平均分子量 MwZ数平均 分子量 Mn比が 1. 5〜5. 5のものが好ましく用いられ、特に好ましくは 2. 0〜5. 0で あり、更【こ好ましく ίま 2. 5〜5. 0であり、更【こ好ましく ίま 3. 0〜5. 0のセノレロースエス テルが好ましく用いられる。  [0068] Further, the cellulose ester used in the present invention preferably has a weight average molecular weight MwZ number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 2.0 to 5.0. More preferably, it is 2.5 to 5.0, and a more preferably 3.0 to 5.0 cenorelose ester is preferably used.
[0069] 本発明で用いられるセルロースエステルの原料セルロースは、木材パルプでも綿花 リンターでもよぐ木材パルプは針葉樹でも広葉樹でもよいが、針葉樹の方がより好ま しい。製膜の際の剥離性の点力もは綿花リンターが好ましく用いられる。これらから作 られたセルロースエステルは適宜混合して、或いは単独で使用することが出来る。  [0069] The raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter. Wood pulp may be coniferous or hardwood, but coniferous is more preferred. Cotton linter is also preferably used for the peelable point force during film formation. Cellulose esters made from these can be mixed appropriately or used alone.
[0070] 例えば、綿花リンター由来セルロースエステル:木材パルプ (針葉樹）由来セルロー スエステル：木材パルプ（広葉樹）由来セルロースエステルの比率が 100： 0： 0、 90： 10:0、 85:15:0、 50:50:0、 20:80:0、 10:90:0、 0:100:0、 0:0:100、 80:10 :10、 85:0:15、 40 :30 :30で用いることが出来る。 [0070] For example, cotton linter-derived cellulose ester: wood pulp (coniferous) -derived cellulose Suester: The ratio of cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50: 50: 0, 20: 80: 0, 10: 90: 0, 0 : 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
[0071] 本発明に係るセルロースエステル榭脂は、 20mlの純水（電気伝導度 0. 1 μ S/c m以下、 pH6. 8)に lg投入し、 25°C、 lhr、窒素雰囲気下にて攪拌した時の pHが 6 〜7、電気伝導度が 1〜： LOO/z SZcmであることが好ましい。 pHが 6未満の場合、残 留有機酸が加熱溶融時にセルロースの劣化を促進させる恐れがあり、 pHが 7より高 い場合、加水分解が促進する恐れがある。また、電気伝導度が 100 SZcm以上の 場合、残留イオンが比較的多く存在するため、加熱溶融時にセルロースを劣化させ る要因になると考えられる。  [0071] The cellulose ester resin according to the present invention is charged into 20 ml of pure water (electrical conductivity of 0.1 μS / cm or less, pH 6.8) at 25 ° C, lhr, under a nitrogen atmosphere. When stirred, the pH is preferably 6 to 7, and the electric conductivity is 1 to: LOO / z SZcm. If the pH is less than 6, the residual organic acid may accelerate cellulose degradation during heating and melting, and if the pH is higher than 7, hydrolysis may accelerate. In addition, when the electrical conductivity is 100 SZcm or more, since a relatively large amount of residual ions are present, it may be a factor that deteriorates cellulose during heating and melting.
[0072] (酸化防止剤）  [0072] (Antioxidant)
本発明に用いられる酸化防止剤につ 、て説明する。  The antioxidant used in the present invention will be described.
[0073] 酸ィ匕防止剤としては、フエノール系酸ィ匕防止剤、リン系酸化防止剤、ィォゥ系酸ィ匕 防止剤、耐熱カ卩ェ安定剤、酸素スカベンジャー等が挙げられ、これらの中でもフエノ ール系酸化防止剤、特にアルキル置換フエノール系酸ィ匕防止剤が好ましい。これら の酸ィ匕防止剤を配合することにより、透明性、耐熱性等を低下させることなぐ成型時 の熱や酸化劣化等による成形体の着色や強度低下を防止出来る。これらの酸化防 止剤は、それぞれ単独で、或いは 2種以上を組み合わせて用いることが出来、その 配合量は、本発明の目的を損なわない範囲で適宜選択される力 セルロースエステ ル榭脂 100質量部に対して好ましくは 0. 001〜5質量部、より好ましくは 0. 01〜1質 量部である。  [0073] Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, phenol-based antioxidants, heat-resistant cache stabilizers, oxygen scavengers, and the like. Phenolic antioxidants, particularly alkyl-substituted phenolic acid inhibitors are preferred. By blending these anti-oxidation agents, coloring and strength reduction of the molded product due to heat and oxidative deterioration during molding can be prevented without reducing transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the amount of the antioxidant is appropriately selected within a range not impairing the object of the present invention. Cellulose ester resin 100 mass The amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to parts.
[0074] 酸ィヒ防止剤としては、ヒンダードフエノール酸ィヒ防止剤化合物は既知の化合物であ り、例えば、米国特許第 4, 839, 405号明細書の第 12〜14欄に記載されているも のなどの、 2, 6—ジアルキルフ ノール誘導体化合物が含まれる。このような化合物 には、以下の一般式（1)のものが含まれる。  [0074] As the acid inhibitor, the hindered phenol acid inhibitor compound is a known compound, and is described in, for example, columns 12 to 14 of US Pat. No. 4,839,405. 2, 6-dialkylphenol derivative compounds, such as Such compounds include those of the following general formula (1).
[0075] [化 1] —般式 (1》
Figure imgf000019_0001
上式中、 Rl、 R2及び R3は、更に置換されている力または置換されていないアルキ ル置換基を表す。ヒンダードフエノール化合物の具体例には、 n—ォクタデシル 3— ( 3, 5—ジ一 t—ブチル 4—ヒドロキシフエ-ル）一プロピオネート、 n—ォクタデシル 3— (3, 5—ジ一 t—ブチル 4—ヒドロキシフエ-ル）一アセテート、 n—ォクタデシル 3, 5—ジ tーブチルー 4ーヒドロキシベンゾエート、 n—へキシル 3, 5—ジ tーブ チルー 4ーヒドロキシフエ-ルペンゾエート、 n—ドデシル 3, 5—ジ—tーブチルー 4 ヒドロキシフエ-ルペンゾエート、ネオードデシル 3— (3, 5—ジ tーブチルー 4ーヒ ドロキシフエ-ル）プロピオネート、ドデシル (3, 5—ジ一 t—ブチル 4—ヒドロキシ フエ-ル）プロピオネート、ェチルひ一（4—ヒドロキシ一 3, 5—ジ一 t—ブチルフエ- ル）イソブチレート、ォクタデシル α—（4ーヒドロキシ 3, 5—ジー t—ブチルフエ- ル)イソブチレート、ォクタデシル α—（4ーヒドロキシ 3, 5—ジ tーブチルー 4ーヒ ドロキシフエ-ル）プロピオネート、 2—（n—ォクチルチオ）ェチル 3, 5 ジー tーブチ ルー 4ーヒドロキシ一べンゾエート、 2 （n—ォクチルチオ）ェチル 3, 5 ジ—tーブ チルー 4ーヒドロキシ—フエ-ルアセテート、 2—（n—ォクタデシルチオ）ェチル 3, 5 ージ—tーブチルー 4ーヒドロキシフエ-ルアセテート、 2 （n—ォクタデシルチオ）ェ チル 3, 5 ジ一 t—ブチル 4 ヒドロキシ一ベンゾエート、 2— (2 ヒドロキシェチ ルチオ）ェチル 3, 5—ジー tーブチルー 4ーヒドロキシベンゾエート、ジェチルダリコー ルビス—（3, 5 ジ— t ブチル—4 ヒドロキシ—フエ-ル）プロピオネート、 2— (n ーォクタデシルチオ）ェチル 3— (3, 5—ジ tーブチルー 4ーヒドロキシフエ-ル）プ 口ピオネート、ステアルアミド N, N ビス一 [エチレン 3— (3, 5—ジ一 t—ブチル 4 —ヒドロキシフエ-ル）プロピオネート]、 n—ブチルイミノ N, N ビス一 [エチレン 3— (3, 5 ジ— t—ブチル—4 ヒドロキシフエ-ル）プロピオネート]、 2— (2—ステア口 ィルォキシェチルチオ）ェチル 3, 5 ジー tーブチルー 4ーヒドロキシベンゾエート、 2 一（2—ステアロイルォキシェチルチオ）ェチル 7—（3—メチルー 5—t—ブチルー 4 —ヒドロキシフエ-ル）ヘプタノエート、 1, 2 プロピレングリコールビス一 [3— (3, 5 ージー t ブチル 4 ヒドロキシフエニル）プロピオネート]、エチレングリコールビス [0075] [Chemical 1] —General formula (1)
Figure imgf000019_0001
In the above formulae, Rl, R2 and R3 represent a further substituted force or an unsubstituted alkyl substituent. Specific examples of hindered phenol compounds include n-octadecyl 3- (3,5-di-tert-butyl 4-hydroxyphenol) -propionate, n-octadecyl 3- (3,5-di-tert-butyl. 4-hydroxyphenyl) monoacetate, n-octadecyl 3,5-di-tert-butyl 4-hydroxybenzoate, n-hexyl 3,5-di-tert-butyl 4-hydroxyphenol penzoate, n-dodecyl 3,5- Di-tert-butyl-4-hydroxyphenol penzoate, neododecyl 3— (3,5-ditert-butyl-4-hydroxyphenyl) propionate, dodecyl (3,5-ditert-butyl 4-hydroxyphenol) propionate, Ethyl chloride (4-hydroxy-1,3,5-di-tert-butylphenol) isobutyrate, Octadecyl α- (4-hydroxy-3,5-ditert-butylphenol) isobutyrate Octadecyl α- (4-hydroxy 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2- (n-octylthio) ethyl 3,5 di-tert-butyl 4-hydroxy monobenzoate, 2 (n-octylthio) ethyl 3,5 Di-tert-butyl 4-hydroxy-phenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-tert-butyl-4-hydroxyphenyl acetate, 2 (n-octadecylthio) ethyl 3, 5 Di-tert-butyl 4-hydroxymonobenzoate, 2- (2-hydroxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, jetyl alcohol bis- (3,5 di-tert-butyl-4-hydroxy-phenol ) Propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) pionate, Theearamide N, N bis [ethylene 3— (3,5-di-tert-butyl 4-hydroxyphenol) propionate], n-butylimino N, N bis- [ethylene 3— (3,5 di-t— Butyl—4 hydroxyphenyl) propionate], 2— (2-Steal oxychetylthio) ethyl 3,5 di-tert-butyl-4-hydroxybenzoate, 2 (2-stearoyloxychetylthio) ethyl 7— (3-Methyl-5-t-butyl-4 —Hydroxyphenyl) heptanoate, 1, 2 propylene glycol bis [3— (3,5 tert-butyl 4-hydroxyphenyl) propionate], ethylene glycol bis
[3— (3, 5—ジ tーブチルー 4ーヒドロキシフエ-ル）プロピオネート]、ネオペン チルダリコールビス [3— (3, 5—ジ tーブチルー 4ーヒドロキシフエ-ル）プロピオ ネート]、エチレングリコールビス— (3, 5—ジ— t—ブチル—4—ヒドロキシフエ-ルァ セテート）、グリセリン一 1—n—ォクタデカノエートー 2, 3 ビス一（3, 5 ジ一 t—ブ チル一 4—ヒドロキシフエ-ルアセテート）、ペンタエリトリトールーテトラキス一 [3— (3 ' , 5，一ジ一 t—ブチル 4，一ヒドロキシフエ-ル）プロピオネート]、 1, 1, 1—トリメチ ロールエタン―トリス— [3— (3, 5—ジ— t—ブチル—4—ヒドロキシフエ-ル）プロピ ォネート]、ソルビトールへキサ一 [3— (3, 5—ジ一 t—ブチル 4—ヒドロキシフエ- ル）プロピオネート]、 2 ヒドロキシェチル 7— (3—メチル—5— t—ブチル—4 ヒド ロキシフエ-ル）プロピオネート、 2—ステアロイルォキシェチル 7—（3—メチルー 5— tーブチルー 4ーヒドロキシフエ-ル）ヘプタノエート、 1, 6—n—へキサンジオール ビス [ (3，， 5，一ジ一 t ブチル 4—ヒドロキシフエ-ル）プロピオネート]、ペンタエリ トリトールーテトラキス（3, 5—ジ一 t—ブチル 4—ヒドロキシヒドロシンナメート）が含 まれる。上記タイプのヒンダードフエノール系酸ィ匕防止剤化合物は、例えば、 Ciba S pecialty Chemicals力ら、 "Irganoxl076，，及び" IrganoxlOlO"という商品名で 市販されている。  [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], neopentyl tildaricol bis [3-((3,5-di-tert-butyl-4-hydroxyphenol) propionate], ethylene glycol bis- (3, 5—di-t-butyl—4-hydroxyphenolate), glycerin 1—n—octadecanoate 2, 3 bis (3,5 di-t-butyl 1 4-hydroxyphenol— Acetate), pentaerythritol-tetrakis [3— (3 ', 5, di-di-tert-butyl-4, monohydroxyphenol) propionate], 1, 1,1-trimethylolethane-tris- [3— (3,5-di-tert-butyl-4-hydroxyphenol) propionate], sorbitol hex [3- (3,5-ditert-butyl 4-hydroxyphenol) propionate], 2 Hydroxyethyl 7— (3-methyl-5-tert-butyl 4-hydroxyphenyl) propionate, 2-stearoyloxetyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol bis [(3,5,1 Di-tert-butyl 4-hydroxyphenol) propionate], pentaerythritol-tetrakis (3,5-di-tert-butyl 4-hydroxyhydrocinnamate). Hindered phenolic acid antioxidant compounds of the above type are commercially available, for example, under the trade names “Irganoxl076,” and “IrganoxlOlO” from Ciba Specialty Chemicals.
その他の酸化防止剤としては、具体的には、トリスノユルフェ-ルホスフアイト、トリフ ェ-ルホスファイト、トリス（2, 4 ジ— tert—ブチルフエ-ル）ホスファイト等のリン系 酸化防止剤、ジラウリル 3, 3，一チォジプロピオネート、ジミリスチルー 3, 3，ーチォ ジプロピオネート、ジステアリル 3, 3，一チォジプロピオネート、ペンタエリスリチル テトラキス（3 ラウリルチオプロピオネート)等のィォゥ系酸ィ匕防止剤、 2— tert—ブ チル— 6— (3— tert—ブチル—2 ヒドロキシ— 5—メチルベンジル）—4—メチルフ ェ-ルアタリレート、 2— [1— (2 ヒドロキシ— 3、 5 ジ— tert—ペンチルフエ-ル） ェチル] 4, 6—ジ— tert—ペンチルフエ-ルアタリレート等の而熱加工安定剤、特 公平 08— 27508記載の 3, 4 ジヒドロ一 2H—1 ベンゾピラン系化合物、 3, 3，一 スピロジクロマン系化合物、 1, 1—スピロインダン系化合物、モルホリン、チオモルホ リン、チオモルホリンォキシド、チオモルホリンジォキシド、ピぺラジン骨格を部分構造 に有する化合物、特開平 03— 174150記載のジアルコキシベンゼン系化合物等の 酸素スカベンジャー等が挙げられる。これら酸ィ匕防止剤の部分構造が、ポリマーの一 部、或いは規則的にポリマーへペンダントされていても良ぐ可塑剤、酸捕捉剤、紫 外線吸収剤等の添加剤の分子構造の一部に導入されていても良い。 Specific examples of other antioxidants include phosphorous antioxidants such as trisnoylphenol phosphite, triphenyl phosphite, tris (2,4 di-tert-butylphenol) phosphite, dilauryl 3, 3, 1-dipropionate, dimyristyl 3, 3, -thio dipropionate, distearyl 3, 3, 1-didipropionate, pentaerythrityl tetrakis (3 lauryl thiopropionate), etc. tert-Butyl— 6— (3— tert-Butyl-2 hydroxy-5-methylbenzyl) —4-Methylphenol acrylate, 2— [1— (2 Hydroxy-3, 5 Di-tert-pentylphenol- R) Ethyl] 4, 6-di-tert-pentyl-phenol talate, etc., metathermal processing stabilizers, Japanese Patent Publication No. 08-27508 3, 4 dihydro-1 2H-1 benzopyran compounds, 3, 3, 1 Spirodichroman compounds, 1, 1-spiroindane compounds, morpholine, thiomorpho Examples thereof include phosphorus, thiomorpholine oxide, thiomorpholine dioxide, compounds having a piperazine skeleton in the partial structure, oxygen scavengers such as dialkoxybenzene compounds described in JP-A-03-174150, and the like. Part of the molecular structure of additives such as plasticizers, acid scavengers, and ultraviolet absorbers that may be part of the polymer or regularly pendant to the polymer. May be introduced.
[0078] (有機系添加剤） [0078] (Organic additive)
本発明に係る光学フィルムには、セルロースエステル榭脂、可塑剤、酸化防止剤と アルコール系化合物の他に、有機系添加剤を含有させることが好ましい。有機系添 加剤には、酸捕捉剤、光安定剤、紫外線吸収剤、リタ一デーシヨン制御剤、高分子 材料等がある。  The optical film according to the present invention preferably contains an organic additive in addition to cellulose ester resin, a plasticizer, an antioxidant and an alcohol compound. Organic additives include acid scavengers, light stabilizers, UV absorbers, retardation control agents, and polymer materials.
[0079] 以下、添加剤について、更に詳述する。  [0079] Hereinafter, the additives will be described in more detail.
[0080] (酸捕捉剤）  [0080] (Acid scavenger)
酸捕捉剤としては、米国特許第 4, 137, 201号明細書に記載されている酸捕捉剤 としてのエポキシィ匕合物を含んでなるのが好まし 、。このような酸捕捉剤としてのェポ キシィ匕合物は当該技術分野において既知であり、種々のポリグリコールのジグリシジ ルエーテル、特にポリグリコール 1モル当たりに約 8〜40モルのエチレンォキシドなど の縮合によって誘導されるポリグリコール、グリセロールのジグリシジルエーテルなど 、金属エポキシィ匕合物（例えば、塩ィ匕ビ二ルポリマー組成物において、及び塩化ビ- ルポリマー組成物と共に、従来から利用されているもの）、エポキシィ匕エーテル縮合 生成物、ビスフエノール Aのジグリシジルエーテル（即ち、 4, 4，ージヒドロキシジフエ -ルジメチルメタン）、エポキシィ匕不飽和脂肪酸エステル (特に、 2〜22この炭素原子 の脂肪酸の 4〜2個程度の炭素原子のアルキルのエステル（例えば、ブチルェポキ システアレート)など）、及び種々のエポキシィ匕長鎖脂肪酸トリグリセリドなど (例えば、 エポキシィ匕大豆油などの組成物によって代表され、例示され得る、エポキシ化植物 油及び他の不飽和天然油（これらは時としてエポキシィ匕天然グリセリドまたは不飽和 脂肪酸と称され、これらの脂肪酸は一般に 12〜22個の炭素原子を含有している)） が含まれる。特に好ましいのは、市販のエポキシ基含有エポキシド榭脂化合物 EP ON 815c,及び一般式（2)の他のエポキシ化エーテルオリゴマー縮合生成物であ る。 The acid scavenger preferably comprises an epoxy compound as an acid scavenger described in US Pat. No. 4,137,201. Epoxy compounds as such acid scavengers are known in the art and include condensation of various polyglycol diglycidyl ethers, particularly about 8-40 moles of ethylene oxide per mole of polyglycol. Metal glycol epoxy compounds such as polyglycols derived from glycerol, diglycidyl ethers of glycerol (eg, those conventionally used in salt vinyl polymer compositions and with vinyl chloride polymer compositions), Epoxy ether condensation product, diglycidyl ether of bisphenol A (ie 4,4, -dihydroxydiphenol-dimethylmethane), epoxy ester unsaturated fatty acid ester (especially 2-22 of 4 fatty acids of this carbon atom) Esters of alkyls of up to about 2 carbon atoms (eg butylepoxy cysterate) , And various epoxy long chain fatty acid triglycerides and the like (eg, epoxidized vegetable oils and other unsaturated natural oils, which are represented and exemplified by compositions such as epoxy soybean oil, sometimes these These are called natural glycerides or unsaturated fatty acids, and these fatty acids generally contain 12 to 22 carbon atoms)). Particularly preferred are commercially available epoxy group-containing epoxide resin compounds EP ON 815c and other epoxidized ether oligomer condensation products of general formula (2). The
[0081] [化 2] 一般式 (2)  [0081] [Chemical formula 2] General formula (2)
Figure imgf000022_0001
Figure imgf000022_0001
[0082] 上式中、 nは 0〜12に等しい。用いることが出来る更に可能な酸捕捉剤としては、特 開平 5— 194788号公報の段落 87〜105に記載されているものが含まれる。 [0082] In the above formula, n is equal to 0-12. Further possible acid scavengers that can be used include those described in paragraphs 87 to 105 of JP-B-5-194788.
[0083] (光安定剤）  [0083] (Light stabilizer)
光安定剤としては、ヒンダードアミン光安定剤 (HALS)化合物が挙げられ、これは 既知の化合物であり、例えば、米国特許第 4, 619, 956号明細書の第 5〜11欄及 び米国特許第 4, 839, 405号明細書の第 3〜5欄に記載されているように、 2, 2, 6 , 6—テトラアルキルピぺリジンィ匕合物、またはそれらの酸付加塩もしくはそれらと金 属化合物との錯体が含まれる。このような化合物には、以下の一般式 (3)のものが含 まれる。  Light stabilizers include hindered amine light stabilizer (HALS) compounds, which are known compounds, such as columns 5-11 of U.S. Pat.No. 4,619,956 and U.S. Pat. 4, 839, 405, as described in columns 3-5, 2, 2, 6, 6-tetraalkylpiperidine compounds, or their acid addition salts or their metals Complexes with compounds are included. Such compounds include those of general formula (3) below.
[0084] [化 3] 一般式 (3)
Figure imgf000022_0002
上式中、 R1及び R2は、 Hまたは置換基である。ヒンダードアミン光安定剤化合物の 具体例には、 4 ヒドロキシ一 2, 2, 6, 6—テトラメチルピペリジン、 1—ァリル一 4 ヒ ドロキシ一 2, 2, 6, 6—テトラメチルピペリジン、 1—ベンジル一 4 ヒドロキシ一 2, 2 , 6, 6—テトラメチルピペリジン、 1— (4— t—ブチル 2 ブテュル）一 4 ヒドロキシ - 2, 2, 6, 6—テトラメチルピペリジン、 4ーステアロイルォキシー 2, 2, 6, 6—テトラ メチルビペリジン、 1ーェチルー 4 サリチロイルォキシー 2, 2, 6, 6—テトラメチルピ ペリジン、 4—メタクリロイルォキシ— 1, 2, 2, 6, 6 ペンタメチルピペリジン、 1, 2, 2 , 6, 6—ペンタメチルピペリジンー4ーィルー j8 (3, 5—ジ tーブチルー 4ーヒドロキ シフエ-ル） プロピオネート、 1一べンジルー 2, 2, 6, 6—テトラメチルー 4ーピペリ ジ-ルマレイネート（maleinate)、（ジー 2, 2, 6, 6—テトラメチルピペリジン 4ーィ ル） アジペート、（ジ 2, 2, 6, 6—テトラメチルピペリジンー4 ィル）ーセバケート 、（ジ—1, 2, 3, 6—テトラメチルー 2, 6 ジェチルーピペリジンー4 ィル）ーセバ ケート、（ジ一 1—ァリル一 2, 2, 6, 6—テトラメチル一ピぺリジン一 4—ィル）一フタレ ート、 1 ァセチルー 2, 2, 6, 6—テトラメチルピペリジンー4ーィルーアセテート、トリ メリト酸一トリー（2, 2, 6, 6—テトラメチルピペリジンー4 ィル）エステル、 1—アタリ ロイルー 4 ベンジルォキシー 2, 2, 6, 6—テトラメチルピペリジン、ジブチルーマ口 ン酸ージ一（1, 2, 2, 6, 6 ペンタメチルーピペリジン 4 ィル） エステル、ジべ ンジルーマロン酸ージ一（1, 2, 3, 6—テトラメチルー 2, 6 ジェチルーピペリジン 4一ィル）一エステル、ジメチルービス一 （2, 2, 6, 6—テトラメチルピペリジンー4 ーォキシ）ーシラン，トリスー（1 プロピル 2, 2, 6, 6—テトラメチルピペリジンー4 —ィル）一ホスフィット、トリス一（1—プロピル一 2, 2, 6, 6—テトラメチルピペリジン一 4—ィル）一ホスフェート， N, N，一ビス一（2, 2, 6, 6—テトラメチルピペリジン一 4— ィル）一へキサメチレン一 1, 6 ジァミン、 N, N，一ビス一（2, 2, 6, 6—テトラメチル ピぺリジン一 4—ィル）一へキサメチレン一 1, 6 ジァセトアミド、 1—ァセチルー 4— ( N シクロへキシルァセトアミド） 2, 2, 6, 6—テトラメチルーピペリジン、 4一べンジ ルア — 2, 2, 6, 6—テ卜ラメチルピぺジジン、 N, N，—ビス—（2, 2, 6, 6—テ卜ラメ チルピペリジン— 4—ィル） N, N，—ジブチル—アジパミド、 N, N，—ビス—（2, 2 , 6, 6—テトラメチルピペリジン一 4—ィル） N, N， 一ジシクロへキシル一（2 ヒドロ キシプロピレン）、 N, N'—ビス一 (2, 2, 6, 6—テトラメチルピペリジン一 4—ィル） - P キシリレン一ジァミン、 4— (ビス一 2 ヒドロキシェチル）一アミノー 1, 2, 2, 6, 6 ペンタメチルピペリジン、 4ーメタクリルアミドー 1, 2, 2, 6, 6 ペンタメチルピペリ ジン、 at—シァノ一 13—メチル一 13 - [N— (2, 2, 6, 6—テトラメチルピペリジン一 4 —ィル）]—アミノーアクリル酸メチルエステル。好ましいヒンダードアミン光安定剤の 例には、以下の HALS - 1及び HALS - 2が含まれる。 [0086] [化 4] [0084] [Chemical formula 3] General formula (3)
Figure imgf000022_0002
In the above formula, R1 and R2 are H or a substituent. Specific examples of hindered amine light stabilizer compounds include: 4-hydroxy-1,2,2,6,6-tetramethylpiperidine, 1-aryl-1, hydroxyl 2,2,6,6-tetramethylpiperidine, 1-benzyl 4-hydroxy-1,2,2,6,6-tetramethylpiperidine, 1- (4-tert-butyl-2-butyr) mono-4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy 2,2 , 6, 6-Tetramethylbiperidine, 1-ethyl-4-salicyloyloxy 2, 2, 6, 6-tetramethylpi Peridine, 4-methacryloyloxy-1, 2, 2, 6, 6 Pentamethylpiperidine, 1, 2, 2, 6, 6-Pentamethylpiperidine-4-yl j8 (3,5-di-tert-butyl-4-hydroxyphene- Propionate, 1 Benzylue 2, 2, 6, 6—Tetramethyl-4-piperyl di-maleinate, (G 2, 2, 6, 6-Tetramethylpiperidine 4-yl) Adipate, (Di 2, 2, 6, 6-tetramethylpiperidine-4-yl) -sebacate, (di-1, 2, 3, 6-tetramethyl-2, 6 jetyl-piperidine-4-yl) -sebacate, (di-1,2-aryl) , 2, 6, 6-tetramethyl 1-piperidine 1-yl) 1 phthalate, 1 acetyl 2, 2, 6, 6-tetramethyl piperidine 4-yl acetate, 1 m of trimellitic acid ( 2, 2, 6, 6-tetramethylpiperidine-4-yl) ester, 1-a Reloylux 4 Benzyloxy 2, 2, 6, 6—Tetramethylpiperidine, dibutylomalic acid diester (1, 2, 2, 6, 6 Pentamethylpiperidine 4-yl) Ester, dibenzylrumalonic acid dione (1, 2, 3, 6-Tetramethyl-2, 6 Jetyl-piperidine 4-yl) monoester, dimethyl-bis- (2, 2, 6, 6-tetramethylpiperidine-4-oxy) -silane, Tris- (1 propyl 2, 2, 6, 6-tetramethylpiperidine-4-yl) monophosphite, tris-mono (1-propyl-1,2,2,6,6-tetramethylpiperidine-4-yl) monophosphate, N, N, 1-bis (2, 2, 6, 6-tetramethylpiperidine 1-yl) 1-hexamethylene 1, 6-diamin, N, N, 1-bis (2, 2, 6, 6-tetramethyl pipette L-lysine 4-yl) monohexamethylene 1, 1, 6-diacetamide, 1-acetylー 4— (N cyclohexylacetamide) 2, 2, 6, 6—Tetramethyl-piperidine, 4 Benzylua — 2, 2, 6, 6—Tetramethylpiperidine, N, N, — Bis- (2, 2, 6, 6-tetramethylpiperidine-4-yl) N, N, -dibutyl-adipamide, N, N, -bis- (2, 2, 6, 6-tetramethylpiperidine 1-yl) N, N, 1-dicyclohexyl 1- (2-hydroxypropylene), N, N'-bis 1- (2, 2, 6, 6-tetramethylpiperidine 1-yl)-P xylylene 1-diamin, 4- (bis-2-hydroxyethyl) mono-amino-1, 2, 2, 6, 6 pentamethylpiperidine, 4-methacrylamide-1, 2, 2, 6, 6 pentamethylpiperidine, at- Cyan 13-methyl 1 13-[N- (2, 2, 6, 6-tetramethylpiperidine 1-yl)]-amino-acrylic acid methyl ester. Examples of preferred hindered amine light stabilizers include the following HALS-1 and HALS-2. [0086] [Chemical 4]
HALS— 1) HALS— 1)
Figure imgf000024_0001
Figure imgf000024_0001
[0087] これらのヒンダードアミン系耐光安定剤は、それぞれ単独で、或 、は 2種以上を組 み合わせて用いることが出来、またこれらヒンダードアミン系耐光安定剤と可塑剤、酸 捕捉剤、紫外線吸収剤等の添加剤と併用しても、添加剤の分子構造の一部に導入 されていても良い。その配合量は、本発明の目的を損なわない範囲で適宜選択され る力 セルロースエステル榭脂 100質量部に対して好ましくは 0. 01〜20質量部、よ り好ましくは 0. 02〜15質量部、特に好ましくは 0. 05〜10質量部である。 [0087] These hindered amine light resistance stabilizers can be used alone or in combination of two or more, and these hindered amine light resistance stabilizers and plasticizers, acid scavengers, ultraviolet absorbers can be used. These additives may be used in combination or may be introduced into a part of the additive molecular structure. The compounding amount is appropriately selected within the range not impairing the object of the present invention. The cellulose ester resin preferably has a mass of 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass with respect to 100 parts by mass. Particularly preferred is 0.05 to 10 parts by mass.
[0088] (紫外線吸収剤）  [0088] (UV absorber)
紫外線吸収剤としては、偏光子や表示装置の紫外線に対する劣化防止の観点か ら、波長 370nm以下の紫外線の吸収能に優れており、かつ液晶表示性の観点から 、波長 400nm以上の可視光の吸収が少ないものが好ましい。例えば、ォキシベンゾ フエノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベン ゾフエノン系化合物、シァノアクリレート系化合物、ニッケル錯塩系化合物等を挙げる ことが出来るが、ベンゾフエノン系化合物や着色の少ないベンゾトリアゾール系化合 物が好ましい。また、特開平 10— 182621号公報、特開平 8— 337574号公報記載 の紫外線吸収剤、特開平 6— 148430号公報記載の高分子紫外線吸収剤を用いて ちょい。  As an ultraviolet absorber, it is excellent in the ability to absorb ultraviolet light with a wavelength of 370 nm or less from the viewpoint of preventing the polarizer and the display device from being deteriorated by ultraviolet light, and from the viewpoint of liquid crystal display, it absorbs visible light with a wavelength of 400 nm or more. Those with less are preferred. Examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, etc., but benzophenone compounds and less colored benzotriazole compounds Compounds are preferred. Also, use ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574, and polymer ultraviolet absorbers described in JP-A-6-148430.
[0089] 有用なベンゾトリアゾール系紫外線吸収剤の具体例として、 2— (2' —ヒドロキシ— 5' —メチルフエ-ル）ベンゾトリアゾール、 2— (2' —ヒドロキシ一 3' , 5' —ジ一 t ert—ブチルフエ-ル）ベンゾトリアゾール、 2—（2' —ヒドロキシ—3' —tert—ブチ ルー 5' —メチルフエ-ル）ベンゾトリアゾール、 2— (2' —ヒドロキシ一 3' , 5' - ジ—tert ブチルフエ-ル） 5 クロ口べンゾトリァゾール、 2—（2' —ヒドロキシー 3' —(3 " , 5 Q" —テトラヒドロフタルイミドメチル） 5, —メチルフエニル )ベンゾ卜リァゾール、 2, 2—メチレンビス（4— (1, 1, 3, 3—テ卜ラメチルブチル）—6 — (2H ベンゾトリアゾール 2—ィル）フエノール）、 2— (2' —ヒドロキシ一 3' t ert—ブチル 5' —メチルフエ-ル） 5 クロ口べンゾトリァゾール、 2— (2H ベ ンゾトリァゾールー 2 ィル）ー6 （直鎖及び側鎖ドデシル）ー4 メチルフエノール、 ォクチル— 3—〔3— tert—ブチル 4 ヒドロキシ— 5— (クロ口 2H ベンゾトリア ゾール 2 ィル）フエ-ル〕プロピオネートと 2 ェチルへキシル 3—〔 3— tert - ブチル 4 ヒドロキシ 5— (5 クロ口一 2H ベンゾトリアゾール - 2 ィル）フエ -ル〕プロピオネートの混合物等を挙げることが出来る力 これらに限定されない。 [0089] Specific examples of useful benzotriazole-based UV absorbers include 2- (2'-hydroxy-5'-methylphenol) benzotriazole, 2- (2'-hydroxy-1 3 ', 5'-di-1 t ert—Butylphenol) benzotriazole, 2— (2 ′ —Hydroxy-3 ′ —tert—Butyl 5 '—methylphenol) benzotriazole, 2— (2 ′ —hydroxyl 3 ′, 5′-di-tert butylphenol) 5 clobenzobenzotriazole, 2— (2 ′ —hydroxy-3 ′ — (3 ", 5 Q" —tetrahydrophthalimidomethyl) 5, —methylphenyl) benzotriazole, 2, 2-methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) —6 — (2H benzotriazole 2- 2) (2'-hydroxy 1 3 'tert-butyl 5'-methyl phenol) 5 clobenzobenzotriazole, 2- (2H benzotriazole 2-yl) -6 (directly) Chain and side chain dodecyl) -4-methylphenol, octyl-3- [3-tert-butyl 4-hydroxy-5- (clo-H 2H benzotriazol 2-yl) phenol] propionate and 2-ethylhexyl 3- [3 — Tert-butyl 4-hydroxy 5— (5 black mouth 2H-benzotriazol - 2 I le) Hue - le] and a mixture such as propionate not force limitation possible.
[0090] また、市販品として、チヌビン (TINUVIN) 109、チヌビン (TINUVIN) 171、チヌ ビン (TINUVIN) 360 ( 、ずれもチノく'スペシャルティ一ケミカルズ社製）を用いること も出来る。 [0090] Further, as commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 360 (manufactured by Specialty One Chemicals Co., Ltd.) can also be used.
[0091] ベンゾフエノン系化合物の具体例として、 2, 4 ジヒドロキシベンゾフエノン、 2, 2'  [0091] Specific examples of benzophenone compounds include 2, 4 dihydroxybenzophenone, 2, 2 '
—ジヒドロキシ一 4—メトキシベンゾフエノン、 2 ヒドロキシ一 4—メトキシ一 5—スルホ ベンゾフエノン、ビス（2 メトキシ 4 ヒドロキシ 5 ベンゾィルフエ-ルメタン）等 を挙げることが出来る力 これらに限定されるものではない。  —Dihydroxy-4-methoxybenzophenone, 2-hydroxy-1-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylmethane), and the like.
[0092] 本発明においては、紫外線吸収剤は 0. 1 20質量％添加することが好ましぐ更 に 0. 5〜： LO質量％添加することが好ましぐ更に 1 5質量％添加することが好まし い。これらは 2種以上を併用してもよい。  [0092] In the present invention, 0.1 to 20% by mass of the UV absorber is preferably added, and more preferably 0.5 to: 15% by mass of LO is preferably added. Is preferred. Two or more of these may be used in combination.
[0093] (リタ デーシヨン制御剤）  [0093] (Rita determination control agent)
本発明の光学フィルムにお 、て配向膜を形成して液晶層を設け、偏光板保護フィ ルムと液晶層由来のリタ デーシヨンを複合ィ匕して光学補償能を付与して、液晶表 示品質の向上するような偏光板加工を行ってもよい。リタ デーシヨンを調節するた めに添加する化合物は、欧州特許 911, 656A2号明細書に記載されているような、 二つ以上の芳香族環を有する芳香族化合物をリタ デーシヨン制御剤として使用す ることも出来る。また二種類以上の芳香族化合物を併用してもよい。該芳香族化合物 の芳香族環には、芳香族炭化水素環に加えて、芳香族性へテロ環を含む。芳香族 性へテロ環であることが特に好ましぐ芳香族性へテロ環は一般に、不飽和へテロ環 である。中でも 1, 3, 5—トリァジン環が特に好ましい。 In the optical film of the present invention, an alignment film is formed to provide a liquid crystal layer, and a polarizing plate protective film and a retardation derived from the liquid crystal layer are combined to provide an optical compensation capability, thereby providing a liquid crystal display quality. The polarizing plate may be processed so as to improve this. The compound added to adjust the retardation is an aromatic compound having two or more aromatic rings as described in the specification of European Patent 911, 656A2, which is used as a retardation control agent. You can also Two or more aromatic compounds may be used in combination. The aromatic compound The aromatic ring includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. Aromatic heterocycles that are particularly preferred to be aromatic heterocycles are generally unsaturated heterocycles. Of these, a 1, 3, 5-triazine ring is particularly preferred.
[0094] (高分子材料）  [0094] (Polymer material)
本発明の光学フィルムはセルロースエステル以外の高分子材料やオリゴマーを適 宜選択して混合してもよ ヽ。前述の高分子材料やオリゴマーはセルロースエステルと 相溶性に優れるものが好ましぐフィルムにしたときの透過率が 80%以上、更に好ま しくは 90%以上、更に好ましくは 92%以上であることが好ましい。セルロースエステ ル以外の高分子材料やオリゴマーの少なくとも 1種以上を混合する目的は、加熱溶 融時の粘度制御やフィルム加工後のフィルム物性を向上するために行う意味を含ん でいる。この場合は、上述のその他添加剤として含むことが出来る。  In the optical film of the present invention, polymer materials other than cellulose esters and oligomers may be appropriately selected and mixed. The polymer materials and oligomers described above are excellent in compatibility with cellulose esters, and the transmittance when formed into a preferable film is 80% or more, more preferably 90% or more, and more preferably 92% or more. preferable. The purpose of mixing at least one of polymer materials and oligomers other than cellulose ester includes meanings for controlling viscosity during heat melting and improving film physical properties after film processing. In this case, it can be included as the above-mentioned other additives.
[0095] (マット剤）  [0095] (Matting agent)
本発明の光学フィルムは、滑り性を付与するためにマット剤等の微粒子を添加する ことが出来、微粒子としては、無機化合物の微粒子又は有機化合物の微粒子が挙げ られる。マット剤はできるだけ微粒子のものが好ましぐ微粒子としては、例えば、二酸 化ケィ素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、力 ォリン、タルク、焼成ケィ酸カルシウム、水和ケィ酸カルシウム、ケィ酸アルミニウム、 ケィ酸マグネシウム、リン酸カルシウム等の無機微粒子や架橋高分子微粒子を挙げ ることが出来る。中でも、ニ酸ィ匕ケィ素がフィルムのヘイズを低く出来るので好ましい 。ニ酸ィ匕ケィ素のような微粒子は有機物により表面処理されている場合が多いが、こ のようなものはフィルムのヘイズを低下出来るため好ましい。  In the optical film of the present invention, fine particles such as a matting agent can be added in order to impart slipperiness, and examples of the fine particles include inorganic compound fine particles and organic compound fine particles. Examples of the fine particles in which the matting agent is preferably as fine as possible are, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, strength, talc, calcined calcium hydrate, and calcium hydrate hydrate. Inorganic fine particles such as aluminum silicate, magnesium silicate and calcium phosphate, and crosslinked polymer fine particles can be mentioned. Of these, nickel carbonate is preferable because it can reduce the haze of the film. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such particles are preferred because they can reduce the haze of the film.
[0096] 表面処理で好ま 、有機物としては、ハロシラン類、アルコキシシラン類、シラザン、 シロキサンなどが挙げられる。微粒子の平均粒径が大きい方が滑り性効果は大きぐ 反対に平均粒径の小さい方は透明性に優れる。また、微粒子の二次粒子の平均粒 径は 0. 05-1. 0 mの範囲である。好ましい微粒子の二次粒子の平均粒径は 5〜 50nm力 子ましく、更に好ましくは、 7〜14nmである。これらの微粒子はセルロースェ ステルフィルム中では、セルロースエステルフィルム表面に 0. 01〜1. O /z mの凹凸 を生成させる為に好ましく用いられる。微粒子のセルロースエステル中の含有量はセ ルロースエステルに対して 0. 005〜0. 3質量0 /0が好ましい。 [0096] Preferred organic materials for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like. The larger the average particle size of the fine particles, the greater the sliding effect. On the other hand, the smaller the average particle size, the better the transparency. In addition, the average particle size of the secondary particles of the fine particles is in the range of 0.05 to 1.0 m. The average particle size of the secondary particles of the fine particles is preferably 5 to 50 nm, more preferably 7 to 14 nm. In the cellulose ester film, these fine particles are preferably used in order to produce unevenness of 0.01 to 1. O / zm on the surface of the cellulose ester film. The content of fine particles in cellulose ester is 0. respect cellulose ester 005 to 0.3 mass 0/0 are preferred.
[0097] 二酸化ケイ素の微粒子としては、日本ァエロジル (株）製のァエロジル (AEROSIL ) 200、 200V、 300、 R972、 R972V、 R974、 R202、 R812、 0X50、 TT600等を 挙げ、ること力 S出来、好ましくはァエロジノレ 200V、 R972、 R972V, R974、 R202、 R 812である。これらの微粒子は 2種以上併用してもよい。 2種以上併用する場合、任 意の割合で混合して使用することが出来る。この場合、平均粒径や材質の異なる微 粒子、例えば、ァェロジル 200Vと R972Vを質量比で 0. 1 : 99. 9〜99. 9 : 0. 1の 範囲で使用出来る。 [0097] Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, 0X50, TT600, etc. manufactured by Nippon Aerosil Co., Ltd. Aerogenole 200V, R972, R972V, R974, R202, R812 are preferable. Two or more of these fine particles may be used in combination. When two or more types are used together, they can be mixed and used at an arbitrary ratio. In this case, fine particles having different average particle diameters and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
[0098] 上記マット剤として用いられるフィルム中の微粒子の存在は、別の目的としてフィル ムの強度向上のために用いることも出来る。また、フィルム中の上記微粒子の存在は 、本発明の光学フィルムを構成するセルロースエステル自身の配向性を向上すること も可能である。  [0098] The presence of fine particles in the film used as the matting agent can also be used to improve the strength of the film for another purpose. In addition, the presence of the fine particles in the film can improve the orientation of the cellulose ester itself constituting the optical film of the present invention.
[0099] (溶融流延法による製膜）  [0099] (Film formation by melt casting method)
本発明の光学フィルムは溶融流延法によって形成されることが特徴である。  The optical film of the present invention is characterized by being formed by a melt casting method.
[0100] 溶液流延法において用いられる溶媒 (例えば塩化メチレン等）を用いずに、加熱溶 融する溶融流延による成形法は、更に詳細には、溶融押出成形法、プレス成形法、 インフレーション法、射出成形法、ブロー成形法、延伸成形法等に分類出来る。これ らの中で、機械的強度及び表面精度等に優れる偏光板保護フィルムを得るためには 、溶融押出し法が優れている。  [0100] The molding method based on melt casting in which the solvent used in the solution casting method (for example, methylene chloride, etc.) is melted by heating is more specifically described in the melt extrusion molding method, press molding method, inflation method. The injection molding method, the blow molding method and the stretch molding method can be classified. Among these, in order to obtain a polarizing plate protective film having excellent mechanical strength and surface accuracy, the melt extrusion method is excellent.
[0101] 本発明の光学フィルムの巻きの長さとしては、 500〜5000m力好ましく、 1000〜5 OOOmがより好ましい。幅手両端部には膜厚の 0〜25%の高さのナーリングを設けて 巻き取ることも好まし 、。  [0101] The winding length of the optical film of the present invention is preferably 500 to 5000 m, more preferably 1000 to 5 OOOm. It is also preferable to roll up with a knurling of 0 to 25% of the film thickness at both ends of the width.
[0102] このような非常に長大なフィルムを安定して生産するためには、溶融製膜中に分子 量をいかに低下させないかが重要である。分子量が低下すると、フィルムが脆くなり、 破断が発生しやすくなり、上記のような長さのフィルムを得ることは難しい。分子量の 低下を防ぐためには、前述のような安定化剤を添加するのみならず、材料の購入前 または合成時に混入している溶媒や不純物や、酸素 ·水分などを、溶融プロセス前に なるべく除去しておくことが重要である。溶融流延法による製膜は、溶液流延法と比 ベるとその製膜時の温度が著しく高いため、酸素や水分、或いは化学的に活性な不 純物が混入して 、ると、セルロースエステルの分解が促進されてしまうためである。 [0102] In order to stably produce such a very long film, it is important how the molecular weight is not reduced during melt film formation. When the molecular weight decreases, the film becomes brittle and breaks easily, and it is difficult to obtain a film having the above length. In order to prevent the molecular weight from decreasing, not only the above-mentioned stabilizers are added, but also the solvent and impurities mixed in before the material purchase or synthesis, oxygen and moisture are removed as much as possible before the melting process. It is important to keep it. Film formation by the melt casting method is different from the solution casting method. This is because the temperature at the time of film formation is extremely high, and if oxygen, moisture, or chemically active impurities are mixed in, the decomposition of the cellulose ester is promoted.
[0103] 前記水分や不純物等の揮発成分は、製膜する前に、または溶融前に除去されてい ることが好ましい。この除去する方法は、乾燥による方法が適用出来、加熱法、減圧 法、加熱減圧法等の方法で行うことが出来る。乾燥は空気中または不活性ガスとして 窒素或いはアルゴン等の不活性ガスを選択した雰囲気下で行ってもょ ヽ。これらの 不活性ガスは水や酸素の含有量が低いことが好ましい。酸素濃度は 0. 1%以下であ ることが好ましぐガスの露点は一 30°C以下であることが好ましい。最も好ましくは、実 質的に含有しないことである。これらの公知の乾燥方法を行うとき、フィルム構成材料 が分解しない温度領域で行うことがフィルムの品質上好ましい。例えば、前記乾燥ェ 程で除去した後の残存する水分または不純物は、各々フィルム構成材料の全体に質 量に対して 1質量％以下とすることが好ましぐ更に好ましくは 0. 5質量％以下にする ことである。  [0103] It is preferable that volatile components such as moisture and impurities are removed before film formation or before melting. This removal can be performed by a drying method, such as a heating method, a reduced pressure method, or a heated reduced pressure method. Drying may be performed in air or in an atmosphere where an inert gas such as nitrogen or argon is selected as the inert gas. These inert gases preferably have a low water or oxygen content. It is preferable that the oxygen concentration is 0.1% or less, and the dew point of the gas is preferably 30 ° C or less. Most preferably, it does not contain substantially. When these known drying methods are performed, it is preferable in terms of film quality to be performed in a temperature range in which the film constituting material does not decompose. For example, the moisture or impurities remaining after the removal in the drying step is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total mass of the film constituent materials. It is to make.
[0104] 特にセルロースエステル榭脂の水分は、 0. 3質量0 /0未満のものが好ましく用いられ る。これらの特性値は ASTM— D817— 96により測定することが出来る。セルロース エステルは、更に熱処理することで水分を低減させて 0. 1〜： LOOOppmとして用いる ことが好ましい。 [0104] In particular the moisture of the cellulose ester榭脂are those of less than 0.3 mass 0/0 Ru are preferably used. These characteristic values can be measured by ASTM-D817-96. The cellulose ester is preferably used as 0.1 to: LOOOppm after further heat treatment to reduce moisture.
[0105] また残留有機不純物量は、ヘッドスペースガスクロ法により測定出来る。即ち、既知 量のセルロースエステルフィルムを密閉容器内で 120°Cで 20分間加熱し、その密閉 容器内の気相に含まれる有機溶媒をガスクロマトグラフにより定量する。この結果から 残留有機溶媒量 (％)を算出することが出来る。  [0105] The amount of residual organic impurities can be measured by a headspace gas chromatography method. That is, a known amount of cellulose ester film is heated in a sealed container at 120 ° C. for 20 minutes, and the organic solvent contained in the gas phase in the sealed container is quantified by gas chromatography. From this result, the amount of residual organic solvent (%) can be calculated.
[0106] フィルム構成材料は、製膜前に乾燥することにより、揮発成分の発生を削減すること が出来、榭脂単独、または榭脂とフィルム構成材料の内、榭脂以外の少なくとも 1種 以上の混合物または相溶物に分割して乾燥することが出来る。好ま 、乾燥温度は 80°C以上、かつ乾燥する材料の Tgまたは融点以下であることが好ましい。材料同士 の融着を回避する観点を含めると、乾燥温度は、ょり好ましくは100〜 8—5)で、 更に好ましくは 110〜(Tg— 20) °Cである。好ましい乾燥時間は 0. 5〜24時間、より 好ましくは 1〜18時間、更に好ましくは 1. 5〜12時間である。これらの範囲よりも低い と揮発成分の除去率が低いか、または乾燥に時間が力かり過ぎることがあり、また乾 燥する材料に Tgが存在するときには、 Tgよりも高い乾燥温度に加熱すると、材料が 融着して取り扱いが困難になることがある。乾燥は 1気圧以下で行うことが好ましぐ 特に真空〜 1Z2気圧に減圧しながら行うことが好ましい。乾燥は、榭脂等の材料は 適度に撹拌しながら行うことが好ましぐ乾燥容器内で下部より乾燥空気もしくは乾燥 窒素を送り込みながら乾燥させる流動床方式が、より短時間で必要な乾燥を行うこと が出来るため好ましい。 [0106] The film constituent materials can reduce the generation of volatile components by drying before film formation, and can be reduced by at least one type of resin other than the resin or the resin and the film constituent material. It can be divided into a mixture or a compatible material and dried. Preferably, the drying temperature is 80 ° C. or higher and is not higher than the Tg or melting point of the material to be dried. Including the viewpoint of avoiding the fusion between materials, the drying temperature, Yori at preferably 100-8 -5), and more preferably 110~ (Tg- 20) ° C. The preferred drying time is 0.5 to 24 hours, more preferably 1 to 18 hours, and even more preferably 1.5 to 12 hours. Lower than these ranges And volatile component removal rate may be low, or drying may take too much time, and when Tg is present in the material to be dried, heating to a drying temperature higher than Tg causes the material to fuse. Handling may be difficult. It is preferable to perform the drying at 1 atm or less. It is particularly preferable to perform the drying while reducing the pressure from vacuum to 1 Z2 atm. Drying is preferably carried out with moderate agitation of materials such as fat, etc. The fluidized bed method, in which drying air or dry nitrogen is fed from the bottom in a drying container, performs the necessary drying in a shorter time. It is preferable because it is possible.
[0107] 乾燥工程は 2段階以上に分離してもよぐ例えば予備乾燥工程による材料の保管と 、製膜する直前〜 1週間前の間に行う直前乾燥を行った素材を用いて製膜してもよ い。  [0107] The drying process may be separated into two or more stages. For example, the material is stored using the preliminary drying process, and the film is formed by using the material that has been dried immediately before the film formation to 1 week before. It's okay.
[0108] 乾燥工程によって、フィルム形成材料中の水分 ·不純物等の揮発性成分を除去し た後、フィルム形成材料は個別に、或いは事前に混合 Zペレット化されて、加熱され たバレルに送られ、溶融 ·流動化したのち、 Tダイによってシート状に押出され、例え ば、静電印加法等により冷却ドラム或いはエンドレスベルト等に密着させ、冷却固化 されてシート状に固化し、未延伸シートを得る。これらの工程は、流延工程と呼ばれる  [0108] After removing volatile components such as moisture and impurities in the film-forming material by a drying process, the film-forming material is individually or previously mixed Z pelletized and sent to a heated barrel. After being melted and fluidized, it is extruded into a sheet by a T-die.For example, it is brought into close contact with a cooling drum or an endless belt by an electrostatic application method or the like, cooled and solidified into a sheet, and an unstretched sheet is obtain. These processes are called casting processes
[0109] 得られる光学フィルムの物性を鑑みると、溶融温度（バレル内の温度）は 150〜250 °Cの範囲であることが好ましぐ 180°C〜230°Cであることがより好ましぐ更に好まし くは 190°C〜220°Cである。冷却ドラムの温度は、 90〜150°Cに維持されていること が好ましい。ドラムの温度が 90°C以下であると、ダイ力 押出されたシートが急冷され てフィルム内の構造が膜厚方向に不均一となったり、もろくなつたりすることがあるた め、 90°C以上であることが好ましい。他方、 150°C以上であると、未延伸シートの冷 却速度が遅くなり、生産性が低下するために好ましくな 、。 [0109] Considering the physical properties of the obtained optical film, the melting temperature (temperature in the barrel) is preferably in the range of 150 to 250 ° C, more preferably in the range of 180 ° C to 230 ° C. More preferably, it is 190 ° C to 220 ° C. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C. If the drum temperature is 90 ° C or less, the die force extruded sheet will be cooled rapidly, and the structure in the film may become uneven in the film thickness direction, and may become brittle. The above is preferable. On the other hand, when the temperature is 150 ° C. or higher, the cooling rate of the unstretched sheet is decreased, which is preferable because productivity decreases.
[0110] 本発明の光学フィルムを偏光板保護フィルムとした場合、該保護フィルムの厚さは 1 0〜500 μ m力好まし!/ヽ。特に 10〜： LOO μ m力 ^好ましく、 20〜80 μ m力 ^好ましく、特 に好ましくは 30〜60 /ζ πιである。上記領域よりも光学フィルムが厚いと、例えば、偏 光板保護フィルムとして用いる場合、偏光板加工後の偏光板が厚くなり過ぎ、ノート 型バソコンゃモパイル型電子機器に用 、る液晶表示においては、特に薄型軽量の 目的には適さない。一方、上記領域よりも薄いとフィルムの透湿性が高くなり偏光子 に対して湿度力 保護する能力が低下してしまうために好ましくない。また、位相差フ イルムにおいてはリタ一デーシヨンの発現が困難となるため、好ましくない。 [0110] When the optical film of the present invention is used as a polarizing plate protective film, the thickness of the protective film is preferably 10 to 500 µm! In particular, 10 to: LOO μm force ^ preferably, 20 to 80 μm force ^ preferable, particularly preferably 30 to 60 / ζ πι. When the optical film is thicker than the above region, for example, when used as a polarizing plate protective film, the polarizing plate after polarizing plate processing becomes too thick, especially in the liquid crystal display used for notebook type Bazokon mopile type electronic devices. Thin and lightweight Not suitable for purpose. On the other hand, if it is thinner than the above-mentioned region, the moisture permeability of the film is increased and the ability to protect the polarizer against humidity is reduced, which is not preferable. In addition, in a phase difference film, the expression of retardation is difficult, which is not preferable.
[0111] 尚、溶液流延法ではフィルムの厚みが増えると乾燥 (溶剤除去)負荷が著しく増加 してしまうが、本発明では乾燥 (溶剤除去）工程が不要なため、膜厚が厚いフィルムを 生産性よく製造することが出来る。そのため、必要な位相差の付与や透湿性の低減 等の目的に応じてフィルムの厚みを増やすことが今まで以上にやりやすくなるという 利点がある。また、膜厚の薄いフィルムであっても、このような厚手のフィルムを延伸 することで高い生産性で生産することが出来ると言う効果を有する。尚、延伸した際 のフィルムの膜厚は、延伸倍率と反比例して薄くなる。例えば、未延伸シートが 200 μであった場合、 2倍に延伸すると 100 のフィルムが得られる。  [0111] In the solution casting method, when the film thickness increases, the drying (solvent removal) load increases remarkably. However, in the present invention, a drying (solvent removal) step is not required, so a film with a large film thickness is used. It can be manufactured with high productivity. Therefore, there is an advantage that it is easier than ever to increase the thickness of the film in accordance with the purpose such as imparting a necessary retardation or reducing moisture permeability. In addition, even a thin film can be produced with high productivity by stretching such a thick film. In addition, the film thickness of the stretched film becomes thin in inverse proportion to the draw ratio. For example, if the unstretched sheet is 200μ, stretching 100 times will yield 100 films.
[0112] また、光学フィルム支持体の膜厚変動は、 ± 3%、更に ± 1%、更に好ましくは ±0. [0112] Further, the film thickness variation of the optical film support is ± 3%, more preferably ± 1%, more preferably ± 0.
1%の範囲とすることが好ましい。これらの膜厚変動は、延伸することによって低減す ることが出来る。  A range of 1% is preferable. These film thickness fluctuations can be reduced by stretching.
[0113] 近年の液晶ディスプレイの大型化を鑑みると、偏光板保護フィルムの幅は lm以上 が好ましい。他方で、 4mを超えると装置が大型化し、また搬送が困難となるため、本 発明の光学フィルムの幅は l〜4mが好ましぐ特に好ましくは 1. 4〜2mである。バレ ルから流動してきたセルロースエステルを、 1. 4m以上の幅手に均一にダイから押出 すことは困難であるため、 1. 4m以上の幅を有するフィルムは、横延伸しなければ得 ることは困難である。  [0113] In view of the recent increase in size of liquid crystal displays, the width of the polarizing plate protective film is preferably lm or more. On the other hand, if the length exceeds 4 m, the apparatus becomes large and transport becomes difficult. Therefore, the width of the optical film of the present invention is preferably from 1 to 4 m, particularly preferably from 1.4 to 2 m. Since it is difficult to uniformly extrude cellulose ester that has flowed from the barrel from the die to a width of 1.4 m or more, a film having a width of 1.4 m or more must be obtained unless it is laterally stretched. It is difficult.
[0114] (延伸工程）  [0114] (Stretching process)
次に延伸工程について説明する。この延伸工程での延伸処理は、水処理する場合 の延伸処理にも採用することができる。  Next, the stretching process will be described. The stretching process in this stretching process can also be employed for the stretching process in the case of water treatment.
[0115] 本発明のセルロースエステルを用いた光学フィルムは、溶融温度を低くすることが 出来、溶融押出し後のセルロースエステルの分子量低下を抑えることが出来るため、 搬送時の破断が起こりにくぐ高収率かつ高速に製造出来る。また、溶解時の粘度が 低!、ため力未延伸であっても平面性の良好なフィルムが得られ、更に高倍率延伸が 可能なため、より平面性に優れた光学フィルムを得ることが出来る。更に光学フィルム を生産性よく製造することが出来る。 [0115] The optical film using the cellulose ester of the present invention can lower the melting temperature and suppress the decrease in the molecular weight of the cellulose ester after melt extrusion. Can be manufactured at high speed. In addition, since the viscosity at the time of dissolution is low, a film with good flatness can be obtained even if the force is not stretched, and furthermore, since it can be stretched at a high magnification, an optical film with better flatness can be obtained. . Furthermore optical film Can be manufactured with high productivity.
[0116] バレル力 押出され、冷却ドラムに密着させられた後、冷却ドラム力 剥離されたフ イルムは、横延伸や縦延伸、或いは特開 2004— 226465号公報に開示されている ような、斜め方向の延伸を行うことによって、平面性を向上させ、かつ生産速度を向 上させることが出来る。これらの延伸は、複数回行っても良ぐ複数回行う際には、同 時であっても逐次であっても良い。複数回の延伸を行った際には、全ての延伸倍率 の積が、最終延伸倍率となる。例えば、 2倍の延伸を 2回行えば、最終延伸倍率は 4 倍となる。  [0116] Barrel force After the film is extruded and brought into close contact with the cooling drum, the film peeled off by the cooling drum force is transversely stretched, longitudinally stretched, or slanted as disclosed in JP-A-2004-226465. By stretching in the direction, the flatness can be improved and the production speed can be increased. These stretching operations may be performed a plurality of times, and when performed a plurality of times, they may be performed simultaneously or sequentially. When stretching is performed multiple times, the product of all the stretch ratios becomes the final stretch ratio. For example, if 2 times of stretching is performed twice, the final stretching ratio will be 4 times.
[0117] 尚セルロースエステルは、延伸された方向に対して屈折率が上昇し、遅相軸が形 成される。従って、最終的に得られるフィルムが満たすべき光学特性の範囲内で延 伸倍率は決定される。  [0117] Incidentally, the refractive index of cellulose ester increases in the stretched direction, and a slow axis is formed. Therefore, the stretch ratio is determined within the range of optical characteristics to be satisfied by the finally obtained film.
[0118] フィルム面内の位相差をなるベく低減したい場合には、 2軸延伸することが好ましい 。 1回目の延伸軸と直交する方向に、同倍率程度の延伸を行うにより、 1回目の延伸 による複屈折の発生がキャンセルされ、等方性のフィルムを得ることが出来る。  [0118] In order to reduce the retardation in the film plane as much as possible, biaxial stretching is preferred. By stretching at the same magnification in the direction perpendicular to the first stretching axis, the occurrence of birefringence due to the first stretching is canceled, and an isotropic film can be obtained.
[0119] 他方で、液晶ディスプレイの視野角を拡大する効果のあるような位相差フィルムを 得る場合には、 1回目の延伸と 2回目の延伸の比率を変化させ、どちらか一方の延伸 倍率が他方の延伸倍率よりも大きくなるように延伸することで光学異方性のフィルムを 得ることが出来る。その際の幅手方向と長手方向との延伸倍率比は 1. 1〜2. 0が好 ましぐより好ましくは 1. 2〜1. 5である。  [0119] On the other hand, in order to obtain a retardation film that has the effect of expanding the viewing angle of the liquid crystal display, the ratio of the first stretching and the second stretching is changed, and the stretching ratio of either one is changed. An optically anisotropic film can be obtained by stretching so as to be larger than the other stretching ratio. In this case, the draw ratio between the width direction and the longitudinal direction is preferably 1.1 to 2.0, more preferably 1.2 to 1.5.
[0120] 複数回の延伸を行う際には、長手方向から延伸しても、幅手方向から延伸しても良 いが、幅手方向の延伸工程を経たのちにはフィルムの搬送幅が大きくなり、搬送装置 の大型化を招くため、長手方向の延伸の後に幅手方向の延伸を行うことが好ま 、。  [0120] When stretching a plurality of times, the film may be stretched from the longitudinal direction or from the width direction. However, after the stretching process in the width direction, the conveyance width of the film is large. In order to increase the size of the transport device, it is preferable to perform stretching in the width direction after stretching in the longitudinal direction.
[0121] また、光学フィルムの最終延伸倍率は 1. 5〜4. 0倍であることが好ましい。 1. 5倍 未満では、得られるフィルムの平面性に劣ることがある。他方、 4. 0倍よりも大きく延 伸することは、本発明のセルロースエステルを用いても困難であり、延伸工程中で破 断が起きる可能性が高くなるため好ましくない。より好ましくは 2. 0〜3. 0倍に延伸さ れたものである。  [0121] The final draw ratio of the optical film is preferably 1.5 to 4.0 times. 1. If it is less than 5 times, the obtained film may have poor flatness. On the other hand, stretching more than 4.0 times is difficult even when the cellulose ester of the present invention is used, and it is not preferable because there is a high possibility of breakage during the stretching process. More preferably, it is stretched 2.0 to 3.0 times.
[0122] 最初に、長手方向（MD)の延伸方法について説明する。 [0123] バレル力 押出され、冷却ドラムに密着させられた後、冷却ドラム力 剥離されたフ イルムは、 1つまたは複数のロール群及び Zまたは赤外線ヒーター等の加熱装置を 介して、再度加熱して長手方向に一段または多段 MD延伸してもよ ヽ。 [0122] First, the stretching method in the longitudinal direction (MD) will be described. [0123] Barrel force After being extruded and brought into close contact with the cooling drum, the film peeled off by the cooling drum force is heated again via one or more groups of rolls and a heating device such as Z or an infrared heater. It is possible to extend MD in the longitudinal direction by one or more stages.
[0124] 延伸する際は、本発明のフィルムのガラス転移温度を Tgとすると (Tg— 30)〜(Tg  [0124] When stretching, assuming that the glass transition temperature of the film of the present invention is Tg, (Tg-30) to (Tg
+ 100) °C、より好ましくは (Tg— 20)〜 (Tg + 80) °Cの範囲内で加熱して搬送方向（ 長手方向； MD)或いは幅手方向（TD)に延伸することが好まし 、。（Tg— 20)〜 (Tg + 20) °Cの温度範囲内で横延伸し次 ヽで熱固定することが好ま 、。また延伸工程 の後、緩和処理を行うことも好ましい。  It is preferable to heat in the range of +100) ° C, more preferably in the range of (Tg—20) to (Tg + 80) ° C, and to stretch in the transport direction (longitudinal direction; MD) or width direction (TD). Better ,. It is preferable that the film is transversely stretched within a temperature range of (Tg-20) to (Tg + 20) ° C and then heat-set in the next step. It is also preferable to perform relaxation treatment after the stretching step.
[0125] 光学フィルムの Tgは、フィルムを構成する材料種及び構成する材料の比率によつ て制御することが出来る。本発明の用途においてはフィルムの乾燥時の Tgは 110°C 以上が好ましぐ更に 120°C以上が好ましい。これは液晶表示装置に本発明の光学 フィルムを用いた場合、該フィルムの Tgが上記よりも低いと、使用環境の温度や湿度 、ノ ックライトの熱による影響によって、フィルム内部に固定された分子の配向状態に 影響を与え、リタ一デーシヨン値及びフィルムとしての寸法安定性や形状に大きな変 化を与える可能性が高くなる。また、フィルムの形状を保持出来なくなることがある。 逆に該フィルムの Tgが高過ぎると、フィルム構成材料の分解温度に近づくため製造 しに《なり、フィルム化するときに用いる材料自身の分解によって揮発成分の存在や 着色を呈することがある。従ってガラス転移温度は 180°C以下、より好ましくは 150°C 以下であることが好ましい。このとき、フィルムの Tgiお IS K7121に記載の方法など によって求めることが出来る。  [0125] The Tg of the optical film can be controlled by the type of material constituting the film and the ratio of the constituting materials. In the application of the present invention, the Tg when the film is dried is preferably 110 ° C or more, more preferably 120 ° C or more. This is because when the optical film of the present invention is used in a liquid crystal display device, if the Tg of the film is lower than the above, the temperature of the use environment, the humidity, and the influence of the heat of the knocklight cause the molecules fixed inside the film. The orientation state is affected, and there is a high possibility that the retardation value and the dimensional stability and shape of the film will be greatly changed. In addition, the shape of the film may not be maintained. On the other hand, if the Tg of the film is too high, it will be close to the decomposition temperature of the film constituting material, so that it will be manufactured, and the presence of the volatile components or coloring may occur due to the decomposition of the material itself used when forming the film. Accordingly, the glass transition temperature is preferably 180 ° C or lower, more preferably 150 ° C or lower. At this time, it can be obtained by the method described in Tgi IS K7121 of the film.
[0126] 次に、幅手方向（TD)の延伸方法について説明する。  [0126] Next, a stretching method in the width direction (TD) will be described.
[0127] TD延伸する場合、 2つ以上に分割された延伸領域で温度差を 1〜50°Cの範囲で 順次昇温しながら横延伸すると幅方向の物性の分布が低減でき好ましい。更に横延 伸後、フィルムをその最終 TD延伸温度以下で Tg— 40°C以上の範囲に 0. 01〜5分 間保持すると幅方向の物性の分布が更に低減でき好まし ヽ。  [0127] In the case of TD stretching, it is preferable to perform transverse stretching while sequentially raising the temperature difference in the range of 1 to 50 ° C in a stretching region divided into two or more because the distribution of physical properties in the width direction can be reduced. Furthermore, after transverse stretching, holding the film within the range of Tg—40 ° C or more below the final TD stretching temperature for 0.01 to 5 minutes is preferable because the distribution of physical properties in the width direction can be further reduced.
[0128] 熱固定は、その最終 TD延伸温度より高温で、 Tg— 20°C以下の温度範囲内で通 常 0. 5〜300秒間熱固定する。この際、 2つ以上に分割された領域で温度差が 1〜1 00°Cとなる範囲で順次昇温しながら熱固定することが好ましい。 [0129] 熱固定されたフィルムは通常 Tg以下まで冷却され、フィルム両端のクリップ把持部 分をカットし巻き取られる。この際、最終熱固定温度以下、 Tg以上の温度範囲内で、 横方向及び Zまたは縦方向に 0. 1〜10%弛緩処理することが好ましい。また冷却は 、最終熱固定温度から Tgまでを、毎秒 100°C以下の冷却速度で徐冷することが好ま しい。冷却、弛緩処理する手段は特に限定はなぐ従来公知の手段で行えるが、特 に複数の温度領域で順次冷却しながらこれらの処理を行うことがフィルムの寸法安定 性向上の点で好ましい。尚、冷却速度は、最終熱固定温度を Tl、フィルムが最終熱 固定温度から Tgに達するまでの時間を tとした時、（Ti— Tg) Ztで求めた値である。 [0128] Heat setting is usually performed at a temperature higher than the final TD stretching temperature and within a temperature range of Tg—20 ° C or lower, usually for 0.5 to 300 seconds. At this time, it is preferable to heat-set while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more. [0129] The heat-set film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the transverse direction and the Z or longitudinal direction within a temperature range not higher than the final heat setting temperature and Tg or higher. In addition, it is preferable that cooling is performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C or less per second. Means for cooling and relaxation treatment are not particularly limited, and can be performed by conventionally known means. In particular, it is preferable to carry out these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value obtained by (Ti-Tg) Zt, where Tl is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
[0130] これら熱固定条件、冷却、弛緩処理条件のより最適な条件は、フィルムを構成する セルロースエステルや可塑剤等の添加剤種により異なるので、得られた二軸延伸フィ ルムの物性を測定し、好ま 、特性を有するように適宜調整することにより決定すれ ばよい。  [0130] The more optimal conditions of these heat setting conditions, cooling and relaxation treatment conditions depend on the type of additives such as cellulose ester and plasticizer that make up the film, so the physical properties of the obtained biaxially stretched film were measured. However, it may be determined by appropriately adjusting to have the characteristics.
[0131] 本発明に係る光学フィルムの面内リタ一デーシヨン値 (Ro)及び厚さ方向のリターデ ーシヨン値 (Rth)は、偏光板保護フィルムとして用いる場合には 0≤Ro、 Rth≤70n mであることが好まし!/、。より好ましくは 0≤ Ro≤ 20nm力つ 0≤ Rth≤ 50nmであリ、 より好ましくは 0≤Ro≤ 10nmかつ 0≤Rth≤30nmである。位相差フィルムとして用 ヽる場合に【ま、 30≤Ro≤100mn力つ 70≤Rth≤400mnであリ、より好ましく ίま 35 ≤Ro≤65nn^ 90≤Rth≤180nn efc5。また、 Rthの変動や分布の幅は ± 10 %未満であることが好ましぐより好ましくは ± 5%未満である。更に好ましくは ± 1% 未満であることが好ましぐ最も好ましくは Rthの変動がないことである。  [0131] The in-plane retardation value (Ro) and the retardation value in the thickness direction (Rth) of the optical film according to the present invention are 0≤Ro and Rth≤70 nm when used as a polarizing plate protective film. I prefer to be there! More preferably, 0≤Ro≤20nm, 0≤Rth≤50nm, more preferably 0≤Ro≤10nm and 0≤Rth≤30nm. When using as a retardation film, 30≤Ro≤100mn, 70≤Rth≤400mn, more preferably 35≤Ro≤65nn ^ 90≤Rth≤180nn efc5. In addition, it is preferable that the width of Rth fluctuation and distribution is less than ± 10%, more preferably less than ± 5%. More preferably, it is preferably less than ± 1%, and most preferably, there is no fluctuation of Rth.
[0132] 尚リタ一デーシヨン値 Ro、 Rthは以下の式によって求めることが出来る。  [0132] The retardation values Ro and Rth can be obtained by the following equations.
[0133] Ro= (nx-ny) X d  [0133] Ro = (nx-ny) X d
Rth = ( (nx + ny) /2 - nz) X d  Rth = ((nx + ny) / 2-nz) X d
ここにおいて、 dはフィルムの厚み（nm)、屈折率 nx (フィルムの面内の最大の屈折 率、遅相軸方向の屈折率ともいう）、 ny (フィルム面内で遅相軸に直角な方向の屈折 率）、 nz (厚み方向におけるフィルムの屈折率)である。  Where d is the thickness of the film (nm), refractive index nx (the maximum refractive index in the plane of the film, also referred to as the refractive index in the slow axis direction), ny (in the film plane, the direction perpendicular to the slow axis) Nz (refractive index of the film in the thickness direction).
[0134] 尚、リタ一デーシヨン値 (Ro)、 （Rth)は自動複屈折率計を用いて測定することが出 来る。例えば、 KOBRA— 21ADH (王子計測機器 (株））を用いて、 23°C、 55%RH の環境下で、波長 590nmで求めることが出来る。 [0134] It should be noted that the retardation values (Ro) and (Rth) can be measured using an automatic birefringence meter. For example, using KOBRA-21ADH (Oji Scientific Instruments), 23 ° C, 55% RH Can be obtained at a wavelength of 590 nm.
[0135] また、遅相軸はフィルムの幅手方向 ± 1° もしくは長手方向 ± 1° にあることが好ま しい。より好ましくは幅手方向または長手方向に対してに ±0. 7° 、更に好ましくは 幅手方向または長手方向に対して ±0. 5° である。このような範囲とすることで、得ら れる液晶ディスプレイのコントラストを高めることが出来る。 [0135] The slow axis is preferably in the width direction ± 1 ° of the film or in the longitudinal direction ± 1 °. More preferably, it is ± 0.7 ° with respect to the width direction or the longitudinal direction, and further preferably ± 0.5 ° with respect to the width direction or the longitudinal direction. By setting this range, the contrast of the obtained liquid crystal display can be increased.
[0136] 前記延伸工程における延伸処理は、水処理における延伸処理においても採用する ことができる。 [0136] The stretching treatment in the stretching step can also be employed in the stretching treatment in water treatment.
[0137] 本発明の光学フィルムは製膜工程で実質的に溶媒を使用することがないため、製 膜後巻き取られた光学フィルムに含まれる残留有機溶媒量は安定して 0. 1質量％未 満であり、これによつて従来以上に安定した平面性と Rthをもつ光学フィルムを提供 することが可能である。特に 100m以上の長尺の巻物においても安定した平面性と R thを持つ光学フィルムを提供することが可能となる。該光学フィルムは巻きの長さに つ ヽて ίま特【こ ff¾限 ίまなく、 1500m、 2500m, 5000mであっても好ましく用!ヽられる  [0137] Since the optical film of the present invention does not substantially use a solvent in the film forming process, the amount of residual organic solvent contained in the optical film wound up after film formation is stably 0.1% by mass. Therefore, it is possible to provide an optical film having more stable flatness and Rth than before. In particular, it is possible to provide an optical film having stable flatness and Rth even for a long roll of 100 m or more. The optical film can be used for any length of 1500m, 2500m, or 5000m, regardless of the winding length.
[0138] 溶液流延法で作製された光学フィルムの残留有機溶媒量 (％)を 0. 1質量％以下 とすることは困難であり、そのためには長い乾燥工程が必要である力 この方法によ れば安!ヽコストで極めて低 ヽ残留有機溶媒含有量の光学フィルムを得ることが出来、 光学フィルムとして優れた特性を持つセルロースエステルフィルムを得ることが出来る [0138] It is difficult to reduce the residual organic solvent amount (%) of the optical film produced by the solution casting method to 0.1 mass% or less, and this requires a long drying process. According to this, an optical film having a very low residual organic solvent content can be obtained at low cost, and a cellulose ester film having excellent characteristics as an optical film can be obtained.
[0139] また、製膜工程において、カットされたフィルム両端のクリップ把持部分は、粉砕処 理された後、或いは必要に応じて造粒処理を行った後、同じ品種のフィルム用原料と してまたは異なる品種のフィルム用原料として再利用してもよい。 [0139] Further, in the film forming process, the clip gripping portions at both ends of the cut film are pulverized or granulated as necessary, and then used as film raw materials of the same type. Or you may reuse as a raw material for films of a different kind.
[0140] (機能性層）  [0140] (Functional layer)
本発明の光学フィルム製造に際し、延伸の前及び Z又は後で帯電防止層、ハード コート層、反射防止層、易滑性層、易接着層、防眩層、バリアー層、光学補償層等の 機能性層を塗設してもよい。特に、帯電防止層、ハードコート層、反射防止層、易接 着層、防眩層及び光学補償層から選ばれる少なくとも 1層を設けることが好ましい。こ の際、コロナ放電処理、プラズマ処理、薬液処理等の各種表面処理を必要に応じて 施すことが出来る。 In the production of the optical film of the present invention, functions such as antistatic layer, hard coat layer, antireflection layer, slippery layer, easy adhesion layer, antiglare layer, barrier layer, and optical compensation layer before and after stretching and after Z A sex layer may be applied. In particular, it is preferable to provide at least one layer selected from an antistatic layer, a hard coat layer, an antireflection layer, an easy adhesion layer, an antiglare layer and an optical compensation layer. At this time, various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment are performed as necessary. Can be applied.
[0141] また、前述の可塑剤、紫外線吸収剤、マット剤等の添加物濃度が異なるセルロース 榭脂を含む組成物を共押出しして、積層構造のセルロースエステルフィルムを作製 することも出来る。例えば、スキン層/コア層 Zスキン層といった構成のセルロースェ ステルフィルムを作ることが出来る。例えば、マット剤は、スキン層に多ぐ又はスキン 層のみに入れることが出来る。可塑剤、紫外線吸収剤はスキン層よりもコア層に多く 入れることが出来、コア層のみに入れてもよい。又、コア層とスキン層で可塑剤、紫外 線吸収剤の種類を変更することも出来、例えば、スキン層に低揮発性の可塑剤及び [0141] In addition, a cellulose ester film having a laminated structure can be produced by co-extrusion of a composition containing cellulose resin having different additive concentrations such as the plasticizer, ultraviolet absorber, and matting agent. For example, a cellulose ester film having a structure of skin layer / core layer Z skin layer can be produced. For example, the matting agent can be included in the skin layer more or only in the skin layer. More plasticizers and UV absorbers can be contained in the core layer than in the skin layer, and may be contained only in the core layer. It is also possible to change the types of plasticizers and ultraviolet absorbers in the core layer and skin layer.
Z又は紫外線吸収剤を含ませ、コア層に可塑性に優れた可塑剤、或いは紫外線吸 収性に優れた紫外線吸収剤を添加することも出来る。スキン層とコア層の Tgが異な つていても良ぐスキン層の Tgよりコア層の Tgが低いことが好ましい。又、溶融流延 時のセルロースエステルを含む溶融物の粘度もスキン層とコア層で異なっていても良 ぐスキン層の粘度 >コア層の粘度でも、コア層の粘度≥スキン層の粘度でもよい。 Z or an ultraviolet absorber can be contained, and a plasticizer having excellent plasticity or an ultraviolet absorber having excellent ultraviolet absorption can be added to the core layer. The Tg of the core layer is preferably lower than the Tg of the skin layer, which may be different even if the Tg of the skin layer and the core layer are different. Also, the viscosity of the melt containing the cellulose ester during melt casting may be different between the skin layer and the core layer. The viscosity of the skin layer may be greater than the viscosity of the core layer, or the viscosity of the core layer may be equal to or greater than the viscosity of the skin layer. .
[0142] (偏光板）  [0142] (Polarizing plate)
本発明の光学フィルムを用いた偏光板の作製方法は特に限定されず、一般的な方 法で作製することが出来る。得られた光学フィルムをアルカリ処理し、ポリビニルアル コールフィルムを沃素溶液中に浸漬延伸して作製した偏光子の少なくとも一方の面 に完全鹼ィ匕ポリビュルアルコール水溶液を用 、て本発明の光学フィルムを貼合する 。偏光子の両面に本発明の光学フィルムを偏光板保護フィルムとして貼り合わせても よい。  The method for producing a polarizing plate using the optical film of the present invention is not particularly limited, and can be produced by a general method. The optical film of the present invention is obtained by using a completely poly (polybulal alcohol) aqueous solution on at least one surface of a polarizer prepared by subjecting the obtained optical film to an alkali treatment and immersing and stretching a polyvinyl alcohol film in an iodine solution. Paste. The optical film of the present invention may be bonded to both sides of the polarizer as a polarizing plate protective film.
[0143] 尚、従来の偏光板保護フィルムとしては、コ-カミノルタタック KC8UX、 KC4UX、 KC5UX、 KC8UYゝ KC4UYゝ KC8UCR— 3、 KC8UCR— 4、 KC12UR, KC8 UXW— H、 KC8UYW— HA、 KC8UX— RHA (コ-力ミノルタォプト（株）製）等の セルロースエステルフィルムが用いることが出来る。  [0143] In addition, as the conventional polarizing plate protective film, Co-Camino Nortack KC8UX, KC4UX, KC5UX, KC8UY ゝ KC4UY ゝ KC8UCR-3, KC8UCR-4, KC12UR, KC8 UXW— H, KC8UYW— HA, KC8UX— Cellulose ester films such as RHA (manufactured by Koriki Minoltaput Co., Ltd.) can be used.
[0144] また、上記アルカリ処理の代わりに特開平 6— 94915号、同 6— 118232号に記載 されて 、るような易接着加工を施して偏光板加工を行ってもょ 、。  [0144] Further, instead of the alkali treatment, as described in JP-A-6-94915 and JP-A-6-118232, polarizing plate processing may be performed by performing such easy adhesion processing.
[0145] 偏光板は偏光子及びその両面を保護する保護フィルムで構成されており、更に該 偏光板の一方の面にプロテクトフィルムを、反対面にセパレートフィルムを貼合して構 成することが出来る。プロテクトフィルム及びセパレートフィルムは偏光板出荷時、製 品検査時等において偏光板を保護する目的で用いられる。この場合、プロテクトフィ ルムは、偏光板の表面を保護する目的で貼合され、偏光板を液晶板へ貼合する面 の反対面側に用いられる。又、セパレートフィルムは液晶板へ貼合する接着層をカバ 一する目的で用いられ、偏光板を液晶セルへ貼合する面側に用いられる。 [0145] The polarizing plate is composed of a polarizer and protective films for protecting both sides of the polarizer. Further, a protective film is bonded to one surface of the polarizing plate, and a separate film is bonded to the other surface. Can be achieved. The protective film and separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protective film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. The separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the surface side of the polarizing plate to be bonded to the liquid crystal cell.
[0146] (液晶表示装置）  [0146] (Liquid crystal display device)
液晶表示装置には通常 2枚の偏光板の間に液晶を含む基板が配置されているが、 本発明の光学フィルムを適用した偏光板保護フィルムは平面性'リタ一デーシヨンの 均一性が高いため、どの部位に配置しても優れた表示性が得られる。液晶表示装置 の表示側最表面の偏光板保護フィルムには、クリアハードコート層、防眩層、反射防 止層等が設けられた偏光板保護フィルムをこの部分に用いることが好ましい。また光 学補償層を設けた偏光板保護フィルムや、延伸操作等によりそれ自身に適切な光学 補償能を付与した偏光板保護フィルムの場合には、液晶セルと接する部位に配置す ることで、優れた表示性が得られる。特にマルチドメイン型の液晶表示装置、より好ま しくは複屈折モードによってマルチドメイン型の液晶表示装置に使用することが本発 明の効果をより発揮することが出来る。  In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the optical film of the present invention is applied has high flatness and uniformity of retardation. Excellent display properties can be obtained even if it is placed on the site. A polarizing plate protective film provided with a clear hard coat layer, an antiglare layer, an antireflective layer, or the like is preferably used for the polarizing plate protective film on the display side outermost surface of the liquid crystal display device. In addition, in the case of a polarizing plate protective film provided with an optical compensation layer, or a polarizing plate protective film provided with appropriate optical compensation ability by itself, such as stretching operation, it can be disposed at a site in contact with the liquid crystal cell. Excellent display properties can be obtained. In particular, the effect of the present invention can be further exerted by using it in a multi-domain liquid crystal display device, more preferably in a multi-domain liquid crystal display device by a birefringence mode.
[0147] マルチドメイン化とは、 1画素を構成する液晶セルを更に複数に分割する方式であ り、視野角依存性の改善 ·画像表示の対称性の向上にも適しており、種々の方式が 報告されている「置田、山内：液晶， 6 (3) , 303 (2002)」。該液晶表示セルは、「山 田、山原:液晶， 7 (2) , 184 (2003)」にも示されており、これらに限定される訳では ない。  [0147] The multi-domain method is a method of dividing the liquid crystal cell that constitutes one pixel into a plurality of parts. It is suitable for improving the viewing angle dependency and improving the symmetry of image display. “Okita, Yamauchi: Liquid Crystal, 6 (3), 303 (2002)”. The liquid crystal display cell is also shown in “Yamada, Yamahara: Liquid Crystal, 7 (2), 184 (2003)”, but is not limited thereto.
[0148] 表示セルの表示品質は、人の観察において左右対称であることが好ましい。従って 、表示セルが液晶表示セルである場合、実質的に観察側の対称性を優先してドメイ ンをマルチ化することが出来る。ドメインの分割は、公知の方法を採用することが出来 、 2分割法、より好ましくは 4分割法によって、公知の液晶モードの性質を考慮して決 定出来る。  [0148] The display quality of the display cell is preferably symmetrical in human observation. Therefore, when the display cell is a liquid crystal display cell, the domain can be multiplied substantially giving priority to the symmetry on the observation side. A known method can be used to divide the domain, and can be determined by a two-division method, more preferably a four-division method in consideration of the properties of the known liquid crystal mode.
[0149] 本発明の偏光板は垂直配向モードに代表される MVA (Multi— domein Vertic al Alignment)モード、特に 4分割された MVAモード、電極配置によってマルチド メイン化された公知の PVA (Patterned Vertical Alignment)モード、電極配置 とカイラル能を融合した CPA (Continuous Pinwheel Alignment)モードに効果 的に用いることが出来る。また、 OCB (Optical Compensated Bend)モードへの 適合においても光学的に二軸性を有するフィルムの提案が開示されており「T. Miya shita, T. Uchida:J. SID, 3 (1) , 29 (1995)」、本発明の偏光板によって表示品 質において、本発明の効果を発現することも出来る。本発明の偏光板を用いることに よって本発明の効果が発現出来れば、液晶モード、偏光板の配置は限定されるもの ではない。 [0149] The polarizing plate of the present invention is a multi-domestic vertical alignment (MVA) mode typified by a vertical alignment mode, in particular, an MVA mode divided into four, and a multi-domain by electrode arrangement. It can be effectively used in the well-known main PVA (Patterned Vertical Alignment) mode and the CPA (Continuous Pinwheel Alignment) mode, which combines electrode arrangement and chirality. In addition, a proposal of an optically biaxial film is also disclosed in conformity with the OCB (Optical Compensated Bend) mode, and “T. Miya shita, T. Uchida: J. SID, 3 (1), 29 (1995) ”, the effect of the present invention can be exhibited in the display quality by the polarizing plate of the present invention. If the effect of the present invention can be exhibited by using the polarizing plate of the present invention, the arrangement of the liquid crystal mode and the polarizing plate is not limited.
[0150] 該液晶表示装置はカラー化及び動画表示用の装置としても高性能であるため、本 発明の光学フィルムを用いた液晶表示装置、特に大型の液晶表示装置の表示品質 は、疲れにくく忠実な動画像表示が可能となる。  [0150] Since the liquid crystal display device has high performance as a device for colorization and moving image display, the display quality of the liquid crystal display device using the optical film of the present invention, particularly a large liquid crystal display device, is less fatigued and faithful. Display of moving images is possible.
実施例  Example
[0151] 以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定され るものではない。  [0151] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.
[0152] 《光学フィルムの作製》 [0152] << Production of optical film >>
実施例 1  Example 1
(組成物 1)  (Composition 1)
セルロースアセテートプロピオネート 1 (重量平均分子量； 200000、ァセチル基置 換度； 1. 95、プロピル基置換度; 0. 75)  Cellulose acetate propionate 1 (weight average molecular weight; 200,000, acetyl substitution degree; 1.95, propyl substitution degree; 0.75)
lOOOOg  lOOOOg
可塑剤  Plasticizer
水溶性：ポリエチレングリコール（数平均分子量 600) lOOOg 疎水性：トリメチロールプロパントリべンゾエート (旭電化工業社製） 500g TINUVIN144 (チノく'スペシャルティ ·ケミカルズ社製） 400g  Water solubility: Polyethylene glycol (number average molecular weight 600) lOOOg Hydrophobicity: Trimethylolpropane tribenzoate (Asahi Denka Kogyo Co., Ltd.) 500g TINUVIN144 (Chinoku's Specialty Chemicals Co., Ltd.) 400g
下記紫外線吸収剤 LA— 31 (旭電化工業社製） 100g R972V (曰本ァエロジル社製） 50g  The following UV absorber LA-31 (Asahi Denka Kogyo Co., Ltd.) 100g R972V (Enomoto Aerosil Co., Ltd.) 50g
[0153] [化 5]
Figure imgf000038_0001
[0153] [Chemical 5]
Figure imgf000038_0001
[0154] 上記組成物 1をヘンシェルミキサーにて 3000rpm、 3minの条件で攪拌し、添加剤 の分散及びセルロースとの混合を行った。得られた混合物の内、一部（20〜30g)は 、融点及び溶融粘度測定用に取り置きした。得られた混合物を、真空乾燥機 (yama to社製 DP41)にて真空ポンプを引きながら、パージ口から露点—40°Cの Nガ [0154] The composition 1 was stirred with a Henschel mixer at 3000 rpm for 3 minutes, and the additive was dispersed and mixed with cellulose. A part (20-30 g) of the obtained mixture was set aside for melting point and melt viscosity measurement. While pulling the vacuum pump with a vacuum dryer (yamato DP41), the resulting mixture was discharged from the purge port with a dew point of -40 ° C N gas.
2 スを注入し、ドライ N雰囲気下、 130°C  2 pours, 130 ° C under dry N atmosphere
2 、 3hrの条件で乾燥を行った。乾燥後の成型 物の水分量をカールフィッシャー水分量測定装置（ダイァインスツルメンッ社製： CA — 06、 VA— 06)を用い電量滴定法にて測定したところ、 120ppmであった。  Drying was performed for 2 to 3 hours. The moisture content of the molded product after drying was 120 ppm when measured by a coulometric titration method using a Karl Fischer moisture measuring device (manufactured by Dia Instruments MEN: CA-06, VA-06).
[0155] 乾燥後の上記混合物を、 Tダイを具備した 2軸成形機に投入し、スクリュー回転数 は 200rpmとし、バレル内の温度 (溶融温度）は 240°Cに設定し、溶融し流動化した セルロースエステル組成物を、 130°Cに保持された冷却ドラム上にキャスティングした 後、流れ方向（MD)に 25%、幅手方向（TD)に 25%延伸を行い（最終延伸倍率は 1 . 56倍）、幅 1500mm、膜厚 80 μ mのロール状光学フィルムを作製した。なお、テン ター保持部分は、端部から裁断した。 [0155] The above mixture after drying is put into a twin-screw molding machine equipped with a T-die, the screw speed is 200 rpm, the temperature in the barrel (melting temperature) is set to 240 ° C, and it is melted and fluidized. After casting the cellulose ester composition on a cooling drum maintained at 130 ° C, it was stretched 25% in the flow direction (MD) and 25% in the width direction (TD) (the final stretch ratio is 1. 56 times), a roll optical film having a width of 1500 mm and a film thickness of 80 μm was produced. The tenter holding part was cut from the end.
[0156] 成形条件；（投入部温度) 80°C [0156] Molding conditions; (input temperature) 80 ° C
(バレル温度） 240°C  (Barrel temperature) 240 ° C
(Tダイ温度） 222°C  (T die temperature) 222 ° C
(スクリュー回転数） 200rpm  (Screw speed) 200rpm
(押出し量) 3kgZhr  (Extruded amount) 3kgZhr
(滞留時間） 3分  (Residence time) 3 minutes
(Tダイリップ） 250 μ m  (T die lip) 250 μm
水処理条件；（水温） 95°C  Water treatment conditions; (water temperature) 95 ° C
テンターにより 1. 001倍幅方向に延伸  Stretched in the direction of 1.001 times by a tenter
図 1記載の水処理装置使用  Use of water treatment equipment shown in Fig. 1
卷取り条件;卷取り口一ラーにて卷取り、ローラー二ップ、ローラー周速を調整するこ とで 100 μ mのフィルムを作製した。 Scratch removal condition: Scratch removal, roller dip, and roller peripheral speed can be adjusted with a single scraper. And made a 100 μm film.
[0157] (ローラー二ップ） 250 μ m [0157] (Roller two cups) 250 μm
(ローラー温度） 130°C  (Roller temperature) 130 ° C
(ローラー周速） 2000mm/min  (Roller peripheral speed) 2000mm / min
実施例 2〜7、比較例 1については、表 1記載の水処理条件とした以外は実施例 1と 同様にして光学フィルムを作製した。  For Examples 2 to 7 and Comparative Example 1, optical films were produced in the same manner as in Example 1 except that the water treatment conditions described in Table 1 were used.
[0158] 《評価》 [0158] << Evaluation >>
作製した実施例 1〜7、比較例 1の光学フィルムを用いて以下の評価を実施した。 (幅手方向の位相差のばらつき）  The following evaluations were performed using the optical films of Examples 1 to 7 and Comparative Example 1 that were produced. (Variation of phase difference in the width direction)
位相差のばらつきは、レターデーシヨン値のばらつき で評価した。 レターデ  Variation in phase difference was evaluated by variation in letter value. Letterde
0  0
ーシヨン値のばらつき AR の測定は、自動副屈折計 KOBRA—21ADH (王子計  -Variation of the measured value AR is measured by the automatic sub-refractometer KOBRA-21ADH (Oji Meter
0  0
測機器社製)を用いて、温度 23°C、湿度 55%RHの環境下で測定し、キーエンス社 製のレーザフォーカス変位計 LT— 8010によりフィルムの膜厚を測定し、その平均膜 厚 dを求め、前述の方法に従って、試料の幅手方向で 10箇所 (3回 Z箇所)測定し、 算出された各箇所のレターデーシヨン値 R (3回測定の平均値）の、最大値および  Measured in an environment with a temperature of 23 ° C and a humidity of 55% RH, and measured the film thickness with a Keyence Laser Focus Displacement Meter LT-8010. The average film thickness d In accordance with the method described above, measure 10 locations in the width direction of the sample (3 times Z locations), and calculate the maximum value and the letter value R (average value of 3 times measurement) at each location.
0  0
最小値の差をレターデーシヨン値のばらつき AR とした。  The difference between the minimum values was taken as the variation AR of the letter values.
0  0
[0159] AR 力 nm以下であれば、画像表示装置にて、色ずれ、ムラのない見やすい表  [0159] If the AR force is nm or less, it is easy to see on the image display device without color misalignment or unevenness.
0  0
示画像が得られる。  A display image is obtained.
(面状むら）  (Surface unevenness)
それぞれの吸収軸が直行するように重ねて配置した 2枚の偏光板 (クロスニコル状 態）の間に製膜したセルロースァシレートフィルムを配置し、フィルムの面状むらを目 視で観察し平面性の評価とした。平面性の悪!、ものは部分的に弱!、光漏れをおこし 、それが面状むらとして観察される。  A cellulose acylate film is placed between two polarizing plates (crossed Nicols state) that are stacked so that their absorption axes are perpendicular to each other, and the surface irregularity of the film is visually observed. Flatness was evaluated. Poor flatness! Some things are weak! Light leaks and is observed as surface irregularities.
A：むらなし B :かすかな濃淡あり C :弱いむらあり D :強いむらあり  A: Uneven B: Slight shading C: Slight unevenness D: Strong unevenness
結果を表 1に示す。  The results are shown in Table 1.
[0160] [表 1] 水処 [0160] [Table 1] Water place
試料 1条件  Sample 1 conditions
延伸倍率 (倍） ¾状む b △ RO(nm)  Stretch ratio (times) ¾ shape b △ RO (nm)
温度 (°C) 時間（分）  Temperature (° C) Time (min)
1 95 1 5 1.001 A 2 本発明  1 95 1 5 1.001 A 2 The present invention
2 95 10 1.001 A 3 本発明  2 95 10 1.001 A 3 The present invention
3 98 3 幅保持 A 2 本発明  3 98 3 Width retention A 2 The present invention
4 98 3 1.001 A 2 本発明  4 98 3 1.001 A 2 The present invention
5 98 10 1.01 A 1 本発明  5 98 10 1.01 A 1 The present invention
6 98 5 1.02 A 1 本発明  6 98 5 1.02 A 1 The present invention
7 98 10 1.1 A 1 本発明  7 98 10 1.1 A 1 The present invention
8 98 1 5 1.15 A 1 本発明  8 98 1 5 1.15 A 1 The present invention
9 90 10 1.001 A 3 本発明  9 90 10 1.001 A 3 The present invention
10 80 15 幅保持 A 4 本発明  10 80 15 Width retention A 4 Present invention
1 1 60 20 幅保持 B 5 本発明  1 1 60 20 Width retention B 5 Present invention
12 一 ― ― C 10  12 1 ― ― C 10
[0161] また、可塑剤について実施した結果を表 2に示す。表 2に記載の試料 13  [0161] Table 2 shows the results of the plasticizer. Samples listed in Table 2 13
試料 5の条件で作成したものである。  It was created under the conditions of Sample 5.
[0162] [表 2]  [0162] [Table 2]
Figure imgf000040_0001
Figure imgf000040_0001
[0163] 《偏光板の作製》  [0163] <Production of polarizing plate>
厚さ 120 μ mのポリビュルアルコールフィルムを、一軸延伸（温度 110°C、延伸倍率 5倍）した。これをヨウ素 0. 075g、ヨウィ匕カリウム 5g、水 lOOgの比率力もなる水溶液 に 60秒間浸漬し、次いでヨウ化カリウム 6g、ホウ酸 7. 5g、水 lOOgの比率力もなる 68 °Cの水溶液に浸漬した。これを水洗、乾燥し偏光子を得た。  A 120 μm-thick polybulal alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). Immerse this in an aqueous solution of 0.075g of iodine, 5g of potassium yowi, and water lOOg for 60 seconds, then soak in an aqueous solution of 68 ° C that also has 6g of potassium iodide, 7.5g of boric acid, and water lOOg. did. This was washed with water and dried to obtain a polarizer.
[0164] 次いで、下記工程 1〜5に従って偏光子と上記作製した試料 1〜18の光学フィルム を各々両面に用いて偏光板を作製した。  [0164] Next, a polarizing plate was produced using the polarizer and the optical films of Samples 1 to 18 prepared on both sides according to the following Steps 1 to 5, respectively.
[0165] 工程 1 : 60°Cの 2モル/ Lの水酸ィ匕ナトリウム溶液に 90秒間浸漬し、次いで水洗し 乾燥して、偏光子と貼合する側を酸ィ匕した前記光学フィルムを得た。 [0166] 工程 2：前記偏光子を固形分 2質量％のポリビュルアルコール接着剤槽中に 1〜2 秒浸潰した。 [0165] Step 1: The optical film in which the side to be bonded to the polarizer is dipped is immersed in a 2 mol / L sodium hydroxide solution at 60 ° C for 90 seconds, then washed with water and dried. Obtained. [0166] Step 2: The polarizer was immersed in a polybulal alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
[0167] 工程 3：工程 2で偏光子に付着した過剰の接着剤を軽く拭き除き、これを工程 1で処 理した各々の光学フィルムの上にのせて積層した。  [0167] Step 3: Excess adhesive adhered to the polarizer in Step 2 was gently wiped, and this was placed on each optical film processed in Step 1 and laminated.
[0168] 工程 4 :工程 3で積層した光学フィルムと偏光子を圧力 20〜30NZcm2、搬送ス ピードは約 2mZ分で貼合した。 [0168] Step 4: The optical film and the polarizer laminated in Step 3 were bonded at a pressure of 20 to 30 NZcm 2 and a conveying speed of about 2 mZ.
[0169] 工程 5： 80°Cの乾燥機中に工程 4で作製した光学フィルムと偏光子とを貼り合わせ た試料を 2分間乾燥し、偏光板を作製した。  [0169] Step 5: A sample obtained by bonding the optical film prepared in Step 4 and the polarizer in a drier at 80 ° C was dried for 2 minutes to prepare a polarizing plate.
[0170] 《液晶表示装置の作製》  [0170] <Production of liquid crystal display device>
視認性評価を行う液晶パネルを以下のようにして作製し、偏光板及び液晶表示装 置としての特性を評価した。  A liquid crystal panel for visibility evaluation was prepared as follows, and the characteristics as a polarizing plate and a liquid crystal display device were evaluated.
[0171] く MVAモード型液晶表示装置の視野角評価〉  [0171] <Viewing angle evaluation of MVA mode liquid crystal display>
富士通製 15型液晶ディスプレイ VL— 1530Sにおいて、該液晶テレビに予め貼合 されて 、た偏光板を剥がし、 MVAモード型液晶セルに上記作製した偏光板をそれ ぞれ液晶セルのガラス面に貼合した。  In the 15-inch liquid crystal display VL-1530S manufactured by Fujitsu, the polarizing plate previously bonded to the liquid crystal television is peeled off, and the above-prepared polarizing plate is bonded to the glass surface of the liquid crystal cell. did.
[0172] その際、液晶セルを挟むようにして、前記作製した各々の偏光板 2枚を偏光板の偏 光軸がもとと変わらないように互いに直交するように貼り付け、偏光板、液晶表示装 置の特性を評価したところ、比較例 1の光学フィルムを用いた偏光板、液晶表示装置 に対して、本発明の光学フィルムを用いた偏光板、液晶表示装置は、コントラストも高 ぐ優れた表示性を示した。これにより、液晶ディスプレイなどの画像表示装置用の偏 光板として有用であり、液晶表示装置としても優れた視認性を提供出来ることが確認 された。さらに長期間の使用でも優れた視認性を有していた。  [0172] At that time, with the liquid crystal cell being sandwiched, the two polarizing plates thus prepared were stuck so as to be orthogonal to each other so that the polarization axis of the polarizing plate was not changed from the original, and the polarizing plate, the liquid crystal display device, and the like. As a result of evaluating the characteristics of the display, the polarizing plate and liquid crystal display device using the optical film of the present invention are superior in contrast to the polarizing plate and liquid crystal display device using the optical film of Comparative Example 1. Showed sex. Thus, it was confirmed that it is useful as a polarizing plate for an image display device such as a liquid crystal display and can provide excellent visibility as a liquid crystal display device. Furthermore, it had excellent visibility even after long-term use.

Claims

請求の範囲 The scope of the claims
[1] 少なくともセルロースエステル榭脂及び可塑剤を加熱溶融させてフィルム状に流延 製膜する光学フィルムの製造方法において、フィルム状に流延製膜した後、水処理 することを特徴とする光学フィルムの製造方法。  [1] In an optical film manufacturing method in which at least cellulose ester resin and a plasticizer are melted by heating and cast into a film, the film is cast into a film and then treated with water. A method for producing a film.
[2] 前記水処理時にフィルムを幅保持または延伸処理することを特徴とする請求の範囲 第 1項記載の光学フィルムの製造方法。  [2] The method for producing an optical film according to [1], wherein the film is subjected to width holding or stretching during the water treatment.
[3] 前記水処理を、 1槽以上の水槽内で行うものであることを特徴とする請求の範囲第 1 項または 2項記載の光学フィルムの製造方法。 [3] The method for producing an optical film according to claim 1 or 2, wherein the water treatment is performed in one or more water tanks.
[4] 前記可塑剤として水溶性可塑剤を使用することを特徴とする請求の範囲第 1項〜第[4] A water-soluble plasticizer is used as the plasticizer.
3項 、ずれかの項記載の光学フィルムの製造方法。 Item 3. The method for producing an optical film according to any one of the items.
[5] 前記可塑剤として水溶性可塑剤および疎水性可塑剤を使用することを特徴とする請 求の範囲第 1項〜第 4項いずれかの項記載の光学フィルムの製造方法。 [5] The method for producing an optical film according to any one of claims 1 to 4, wherein a water-soluble plasticizer and a hydrophobic plasticizer are used as the plasticizer.
[6] 請求の範囲第 1項〜第 5項 、ずれかの項記載の光学フィルムの製造方法で得られる ことを特徴とする光学フィルム。 [6] An optical film obtained by the method for producing an optical film according to any one of claims 1 to 5.
[7] 請求の範囲第 6項記載の光学フィルムを、偏光子を挟む 2枚の偏光板保護フィルム のうち少なくとも一枚として用いたことを特徴とする偏光板。 [7] A polarizing plate comprising the optical film according to claim 6 as at least one of two polarizing plate protective films sandwiching a polarizer.
[8] 請求の範囲第 7項記載の偏光板を用いたことを特徴とする液晶表示装置。 [8] A liquid crystal display device using the polarizing plate according to claim 7.
[9] 少なくともセルロースエステル榭脂および可塑剤を加熱溶融させてフィルム状に流延 製膜する光学フィルムの製造装置において、少なくともフィルム状に流涎製膜するェ 程、水処理工程および卷取り工程を有することを特徴とする光学フィルムの製造装置 [9] In an optical film manufacturing apparatus in which at least a cellulose ester resin and a plasticizer are melted by heating and cast into a film, the water treatment process and the wrinkling process are performed at least in the process of casting the film into a film. An optical film manufacturing apparatus comprising:
PCT/JP2007/052227 2006-03-22 2007-02-08 Optical film, method and apparatus for producing same, polarizing plate, and liquid crystal display WO2007108243A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011155725A2 (en) * 2010-06-09 2011-12-15 주식회사 엘지화학 Device for manufacturing polaroid film, and method for manufacturing same
JP2012161965A (en) * 2011-02-04 2012-08-30 Vision Development Co Ltd Method for manufacturing diamond-resin composite material that includes diamond microparticles
JP2014071201A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Cellulose acylate film, polarizing plate, and liquid crystal display device
US20200316839A1 (en) * 2017-11-20 2020-10-08 Vmi Holland B.V. Cooling apparatus and method for cooling a continuous strip

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000325620A (en) * 1999-05-18 2000-11-28 Adachi Light Co Ltd Ball delivery device for pachinko game machine
JP2004050516A (en) * 2002-07-17 2004-02-19 Fuji Photo Film Co Ltd Method of stretching cellulose acylate film and method of manufacturing retardation plate
JP2004182979A (en) * 2002-11-21 2004-07-02 Toray Ind Inc Thermoplastic cellulose acetate propionate composition and fiber consisting of the composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000352620A (en) * 1999-03-31 2000-12-19 Konica Corp Optical film, polarizing plate and liquid crystal display device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000325620A (en) * 1999-05-18 2000-11-28 Adachi Light Co Ltd Ball delivery device for pachinko game machine
JP2004050516A (en) * 2002-07-17 2004-02-19 Fuji Photo Film Co Ltd Method of stretching cellulose acylate film and method of manufacturing retardation plate
JP2004182979A (en) * 2002-11-21 2004-07-02 Toray Ind Inc Thermoplastic cellulose acetate propionate composition and fiber consisting of the composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011155725A2 (en) * 2010-06-09 2011-12-15 주식회사 엘지화학 Device for manufacturing polaroid film, and method for manufacturing same
WO2011155725A3 (en) * 2010-06-09 2012-05-18 주식회사 엘지화학 Device for manufacturing polaroid film, and method for manufacturing same
US8767296B2 (en) 2010-06-09 2014-07-01 Lg Chem, Ltd. Device for producing polarizing film and method of producing the same
JP2012161965A (en) * 2011-02-04 2012-08-30 Vision Development Co Ltd Method for manufacturing diamond-resin composite material that includes diamond microparticles
JP2014071201A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Cellulose acylate film, polarizing plate, and liquid crystal display device
US20200316839A1 (en) * 2017-11-20 2020-10-08 Vmi Holland B.V. Cooling apparatus and method for cooling a continuous strip
US11654606B2 (en) * 2017-11-20 2023-05-23 Vmi Holland B.V. Cooling apparatus and method for cooling a continuous strip

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